Composition including a glycerol ester including at least two epoxides for treatment of subterranean formations

ABSTRACT

Various embodiments disclosed relate to compositions including a glycerol ester including at least two epoxides for treatment of subterranean formations. In various embodiments, the present invention provides a method of treating a subterranean formation. The method includes placing in a subterranean formation a composition including a glycerol ester that includes at least two epoxides. The composition also includes a hardening agent.

BACKGROUND

The presence of particulate matter, such as sand, in produced fluidsfrom hydrocarbon wells can be problematic. For example, particulates canabrade pumping and other production equipment and reduce the fluidproduction capabilities of the producing zones. Hydrocarbon wells areoften located in subterranean zones that contain unconsolidatedparticulate matter that can migrate out of the well along with oil, gas,water, or other fluids produced by the well. Placing proppant downholeduring hydraulic fracturing operations can result in unconsolidatedproppant that can become entrained with produced fluids.

Sand or proppant consolidation is one of the most convenient and costeffective methods to avoid production of these particulates, such asusing curable resins. However, many curable resins, such as many epoxy-and formaldehyde-based resins, can have negative effects on health andthe environment.

BRIEF DESCRIPTION OF THE FIGURES

The drawings illustrate generally, by way of example, but not by way oflimitation, various embodiments discussed in the present document.

FIG. 1 illustrates a system or apparatus for delivering a composition toa subterranean formation, in accordance with various embodiments.

DETAILED DESCRIPTION OF THE INVENTION

Reference will now be made in detail to certain embodiments of thedisclosed subject matter, examples of which are illustrated in part inthe accompanying drawings. While the disclosed subject matter will bedescribed in conjunction with the enumerated claims, it will beunderstood that the exemplified subject matter is not intended to limitthe claims to the disclosed subject matter.

Values expressed in a range format should be interpreted in a flexiblemanner to include not only the numerical values explicitly recited asthe limits of the range, but also to include all the individualnumerical values or sub-ranges encompassed within that range as if eachnumerical value and sub-range is explicitly recited. For example, arange of “about 0.1% to about 5%” or “about 0.1% to 5%” should beinterpreted to include not just about 0.1% to about 5%, but also theindividual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g.,0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range.The statement “about X to Y” has the same meaning as “about X to aboutY,” unless indicated otherwise. Likewise, the statement “about X, Y, orabout Z” has the same meaning as “about X, about Y, or about Z,” unlessindicated otherwise.

In this document, the terms “a,” “an,” or “the” are used to include oneor more than one unless the context clearly dictates otherwise. The term“or” is used to refer to a nonexclusive “or” unless otherwise indicated.The statement “at least one of A and B” has the same meaning as “A, B,or A and B.” In addition, it is to be understood that the phraseology orterminology employed herein, and not otherwise defined, is for thepurpose of description only and not of limitation. Any use of sectionheadings is intended to aid reading of the document and is not to beinterpreted as limiting; information that is relevant to a sectionheading may occur within or outside of that particular section. A commacan be used as a delimiter or digit group separator to the left or rightof a decimal mark; for example, “0.000,1” is equivalent to “0.0001.”

In the methods of manufacturing described herein, the acts can becarried out in any order without departing from the principles of theinvention, except when a temporal or operational sequence is explicitlyrecited. Furthermore, specified acts can be carried out concurrentlyunless explicit claim language recites that they be carried outseparately. For example, a claimed act of doing X and a claimed act ofdoing Y can be conducted simultaneously within a single operation, andthe resulting process will fall within the literal scope of the claimedprocess.

The term “about” as used herein can allow for a degree of variability ina value or range, for example, within 10%, within 5%, within 1%, orwithin 0% of a stated value or of a stated limit of a range.

The term “substantially” as used herein refers to a majority of, ormostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%,98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more.

The term “organic group” as used herein refers to but is not limited toany carbon-containing functional group. For example, anoxygen-containing group such as an alkoxy group, aryloxy group,aralkyloxy group, oxo(carbonyl) group, a carboxyl group including acarboxylic acid, carboxylate, and a carboxylate ester; asulfur-containing group such as an alkyl and aryl sulfide group; andother heteroatom-containing groups. Non-limiting examples of organicgroups include OR, OOR, OC(O)N(R)₂, CN, CF₃, OCF₃, R, C(O),methylenedioxy, ethylenedioxy, N(R)₂, SR, SOR, SO₂R, SO₂N(R)₂, SO₃R,C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)₂,OC(O)N(R)₂, C(S)N(R)₂, (CH₂)₀₋₂N(R)C(O)R, (CH₂)₀₋₂N(R)N(R)₂,N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)₂, N(R)SO₂R, N(R)SO₂N(R)₂,N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂, N(R)C(S)N(R)₂,N(COR)COR, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, or C(═NOR)R, wherein R canbe hydrogen (in examples that include other carbon atoms) or acarbon-based moiety, and wherein the carbon-based moiety can itself befurther substituted.

The term “substituted” as used herein refers to an organic group asdefined herein or molecule in which one or more hydrogen atoms containedtherein are replaced by one or more non-hydrogen atoms. The term“functional group” or “substituent” as used herein refers to a groupthat can be or is substituted onto a molecule or onto an organic group.Examples of substituents or functional groups include, but are notlimited to, a halogen (e.g., F, Cl, Br, and I); an oxygen atom in groupssuch as hydroxy groups, alkoxy groups, aryloxy groups, aralkyloxygroups, oxo(carbonyl) groups, carboxyl groups including carboxylicacids, carboxylates, and carboxylate esters; a sulfur atom in groupssuch as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups,sulfone groups, sulfonyl groups, and sulfonamide groups; a nitrogen atomin groups such as amines, hydroxyamines, nitriles, nitro groups,N-oxides, hydrazides, azides, and enamines; and other heteroatoms invarious other groups. Non-limiting examples of substituents J that canbe bonded to a substituted carbon (or other) atom include F, Cl, Br, I,OR, OC(O)N(R)₂, CN, NO, NO₂, ONO₂, azido, CF₃, OCF₃, R, O (oxo), S(thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R)₂, SR, SOR,SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR,OC(O)R, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂, (CH₂)₀₋₂N(R)C(O)R,(CH₂)₀₋₂N(R)N(R)₂, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)₂,N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(COR)COR, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, or C(═NOR)R,wherein R can be hydrogen or a carbon-based moiety; for example, R canbe hydrogen, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl,heteroaryl, or heteroarylalkyl.

The term “alkyl” as used herein refers to straight chain and branchedalkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, 1to about 20 carbon atoms, 1 to 12 carbons or, in some embodiments, from1 to 8 carbon atoms. Examples of straight chain alkyl groups includethose with from 1 to 8 carbon atoms such as methyl, ethyl, n-propyl,n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples ofbranched alkyl groups include, but are not limited to, isopropyl,iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and2,2-dimethylpropyl groups. As used herein, the term “alkyl” encompassesn-alkyl, isoalkyl, and anteisoalkyl groups as well as other branchedchain forms of alkyl. Representative substituted alkyl groups can besubstituted one or more times with any of the groups listed herein, forexample, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, andhalogen groups.

The term “alkenyl” as used herein refers to straight and branched chainand cyclic alkyl groups as defined herein, except that at least onedouble bond exists between two carbon atoms. Thus, alkenyl groups havefrom 2 to 40 carbon atoms, or 2 to about 20 carbon atoms, or 2 to 12carbons or, in some embodiments, from 2 to 8 carbon atoms. Examplesinclude, but are not limited to vinyl, —CH═CH(CH₃), —CH═C(CH₃)₂,—C(CH₃)═CH₂, —C(CH₃)═CH(CH₃), —C(CH₂CH₃)═CH₂, cyclohexenyl,cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienylamong others.

The term “acyl” as used herein refers to a group containing a carbonylmoiety wherein the group is bonded via the carbonyl carbon atom. Thecarbonyl carbon atom is also bonded to another carbon atom, which can bepart of an alkyl, aryl, aralkyl cycloalkyl, cycloalkylalkyl,heterocyclyl, heterocyclylalkyl, heteroaryl, heteroarylalkyl group orthe like. In the special case wherein the carbonyl carbon atom is bondedto a hydrogen, the group is a “formyl” group, an acyl group as the termis defined herein. An acyl group can include 0 to about 12-20 or 12-40additional carbon atoms bonded to the carbonyl group. An acyl group caninclude double or triple bonds within the meaning herein. An acryloylgroup is an example of an acyl group. An acyl group can also includeheteroatoms within the meaning here. A nicotinoyl group(pyridyl-3-carbonyl) is an example of an acyl group within the meaningherein. Other examples include acetyl, benzoyl, phenylacetyl,pyridylacetyl, cinnamoyl, and acryloyl groups and the like. When thegroup containing the carbon atom that is bonded to the carbonyl carbonatom contains a halogen, the group is termed a “haloacyl” group. Anexample is a trifluoroacetyl group.

The term “aryl” as used herein refers to cyclic aromatic hydrocarbonsthat do not contain heteroatoms in the ring. Thus aryl groups include,but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl,indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl,naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups.In some embodiments, aryl groups contain about 6 to about 14 carbons inthe ring portions of the groups. Aryl groups can be unsubstituted orsubstituted, as defined herein. Representative substituted aryl groupscan be mono-substituted or substituted more than once, such as, but notlimited to, 2-, 3-, 4-, 5-, or 6-substituted phenyl or 2-8 substitutednaphthyl groups, which can be substituted with carbon or non-carbongroups such as those listed herein.

The term “heterocyclyl” as used herein refers to aromatic andnon-aromatic ring compounds containing three or more ring members, ofwhich one or more is a heteroatom such as, but not limited to, N, O, andS. The term “alkoxy” as used herein refers to an oxygen atom connectedto an alkyl group, including a cycloalkyl group, as are defined herein.Examples of linear alkoxy groups include but are not limited to methoxy,ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and the like. Examples ofbranched alkoxy include but are not limited to isopropoxy, sec-butoxy,tert-butoxy, isopentyloxy, isohexyloxy, and the like. Examples of cyclicalkoxy include but are not limited to cyclopropyloxy, cyclobutyloxy,cyclopentyloxy, cyclohexyloxy, and the like. An alkoxy group can includeone to about 12-20 or about 12-40 carbon atoms bonded to the oxygenatom, and can further include double or triple bonds, and can alsoinclude heteroatoms. For example, an allyloxy group is an alkoxy groupwithin the meaning herein. A methoxyethoxy group is also an alkoxy groupwithin the meaning herein, as is a methylenedioxy group in a contextwhere two adjacent atoms of a structure are substituted therewith.

The term “amine” as used herein refers to primary, secondary, andtertiary amines having, e.g., the formula N(group)₃ wherein each groupcan independently be H or non-H, such as alkyl, aryl, and the like.Amines include but are not limited to R—NH₂, for example, alkylamines,arylamines, alkylarylamines; R₂NH wherein each R is independentlyselected, such as dialkylamines, diarylamines, aralkylamines,heterocyclylamines and the like; and R₃N wherein each R is independentlyselected, such as trialkylamines, dialkylarylamines, alkyldiarylamines,triarylamines, and the like. The term “amine” also includes ammoniumions as used herein.

The term “amino group” as used herein refers to a substituent of theform —NH₂, —NHR, —NR₂, —NR₃ ⁺, wherein each R is independently selected,and protonated forms of each, except for —NR₃ ⁺, which cannot beprotonated. Accordingly, any compound substituted with an amino groupcan be viewed as an amine An “amino group” within the meaning herein canbe a primary, secondary, tertiary, or quaternary amino group. An“alkylamino” group includes a monoalkylamino, dialkylamino, andtrialkylamino group.

The terms “halo,” “halogen,” or “halide” group, as used herein, bythemselves or as part of another substituent, mean, unless otherwisestated, a fluorine, chlorine, bromine, or iodine atom.

The term “haloalkyl” group, as used herein, includes mono-halo alkylgroups, poly-halo alkyl groups wherein all halo atoms can be the same ordifferent, and per-halo alkyl groups, wherein all hydrogen atoms arereplaced by halogen atoms, such as fluoro. Examples of haloalkyl includetrifluoromethyl, 1,1-dichloroethyl, 1,2-dichloroethyl,1,3-dibromo-3,3-difluoropropyl, perfluorobutyl, and the like.

The term “hydrocarbon” as used herein refers to a functional group ormolecule that includes carbon and hydrogen atoms. The term can alsorefer to a functional group or molecule that normally includes bothcarbon and hydrogen atoms but wherein all the hydrogen atoms aresubstituted with other functional groups.

As used herein, the term “hydrocarbyl” refers to a functional groupderived from a straight chain, branched, or cyclic hydrocarbon, and canbe alkyl, alkenyl, alkynyl, aryl, cycloalkyl, acyl, or any combinationthereof.

The term “solvent” as used herein refers to a liquid that can dissolve asolid, liquid, or gas. Non-limiting examples of solvents are silicones,organic compounds, water, alcohols, ionic liquids, and supercriticalfluids.

The term “room temperature” as used herein refers to a temperature ofabout 15° C. to 28° C.

The term “standard temperature and pressure” as used herein refers to20° C. and 101 kPa.

As used herein, “degree of polymerization” is the number of repeatingunits in a polymer.

As used herein, the term “polymer” refers to a molecule having at leastone repeating unit and can include copolymers.

The term “copolymer” as used herein refers to a polymer that includes atleast two different repeating units. A copolymer can include anysuitable number of repeating units.

The term “downhole” as used herein refers to under the surface of theearth, such as a location within or fluidly connected to a wellbore.

As used herein, the term “drilling fluid” refers to fluids, slurries, ormuds used in drilling operations downhole, such as during the formationof the wellbore.

As used herein, the term “stimulation fluid” refers to fluids orslurries used downhole during stimulation activities of the well thatcan increase the production of a well, including perforation activities.In some examples, a stimulation fluid can include a fracturing fluid oran acidizing fluid.

As used herein, the term “clean-up fluid” refers to fluids or slurriesused downhole during clean-up activities of the well, such as anytreatment to remove material obstructing the flow of desired materialfrom the subterranean formation. In one example, a clean-up fluid can bean acidification treatment to remove material formed by one or moreperforation treatments. In another example, a clean-up fluid can be usedto remove a filter cake.

As used herein, the term “fracturing fluid” refers to fluids or slurriesused downhole during fracturing operations.

As used herein, the term “spotting fluid” refers to fluids or slurriesused downhole during spotting operations, and can be any fluid designedfor localized treatment of a downhole region. In one example, a spottingfluid can include a lost circulation material for treatment of aspecific section of the wellbore, such as to seal off fractures in thewellbore and prevent sag. In another example, a spotting fluid caninclude a water control material. In some examples, a spotting fluid canbe designed to free a stuck piece of drilling or extraction equipment,can reduce torque and drag with drilling lubricants, preventdifferential sticking, promote wellbore stability, and can help tocontrol mud weight.

As used herein, the term “completion fluid” refers to fluids or slurriesused downhole during the completion phase of a well, including cementingcompositions.

As used herein, the term “remedial treatment fluid” refers to fluids orslurries used downhole for remedial treatment of a well. Remedialtreatments can include treatments designed to increase or maintain theproduction rate of a well, such as stimulation or clean-up treatments.

As used herein, the term “abandonment fluid” refers to fluids orslurries used downhole during or preceding the abandonment phase of awell.

As used herein, the term “acidizing fluid” refers to fluids or slurriesused downhole during acidizing treatments. In one example, an acidizingfluid is used in a clean-up operation to remove material obstructing theflow of desired material, such as material formed during a perforationoperation. In some examples, an acidizing fluid can be used for damageremoval.

As used herein, the term “cementing fluid” refers to fluids or slurriesused during cementing operations of a well. For example, a cementingfluid can include an aqueous mixture including at least one of cementand cement kiln dust. In another example, a cementing fluid can includea curable resinous material such as a polymer that is in an at leastpartially uncured state.

As used herein, the term “water control material” refers to a solid orliquid material that interacts with aqueous material downhole, such thathydrophobic material can more easily travel to the surface and such thathydrophilic material (including water) can less easily travel to thesurface. A water control material can be used to treat a well to causethe proportion of water produced to decrease and to cause the proportionof hydrocarbons produced to increase, such as by selectively bindingtogether material between water-producing subterranean formations andthe wellbore while still allowing hydrocarbon-producing formations tomaintain output.

As used herein, the term “packer fluid” refers to fluids or slurriesthat can be placed in the annular region of a well between tubing andouter casing above a packer. In various examples, the packer fluid canprovide hydrostatic pressure in order to lower differential pressureacross the sealing element, lower differential pressure on the wellboreand casing to prevent collapse, and protect metals and elastomers fromcorrosion.

As used herein, the term “fluid” refers to liquids and gels, unlessotherwise indicated.

As used herein, the term “subterranean material” or “subterraneanformation” refers to any material under the surface of the earth,including under the surface of the bottom of the ocean. For example, asubterranean formation or material can be any section of a wellbore andany section of a subterranean petroleum- or water-producing formation orregion in fluid contact with the wellbore. Placing a material in asubterranean formation can include contacting the material with anysection of a wellbore or with any subterranean region in fluid contacttherewith. Subterranean materials can include any materials placed intothe wellbore such as cement, drill shafts, liners, tubing, casing, orscreens; placing a material in a subterranean formation can includecontacting with such subterranean materials. In some examples, asubterranean formation or material can be any below-ground region thatcan produce liquid or gaseous petroleum materials, water, or any sectionbelow-ground in fluid contact therewith. For example, a subterraneanformation or material can be at least one of an area desired to befractured, a fracture or an area surrounding a fracture, and a flowpathway or an area surrounding a flow pathway, wherein a fracture or aflow pathway can be optionally fluidly connected to a subterraneanpetroleum- or water-producing region, directly or through one or morefractures or flow pathways.

As used herein, “treatment of a subterranean formation” can include anyactivity directed to extraction of water or petroleum materials from asubterranean petroleum- or water-producing formation or region, forexample, including drilling, stimulation, hydraulic fracturing,clean-up, acidizing, completion, cementing, remedial treatment,abandonment, and the like.

As used herein, a “flow pathway” downhole can include any suitablesubterranean flow pathway through which two subterranean locations arein fluid connection. The flow pathway can be sufficient for petroleum orwater to flow from one subterranean location to the wellbore orvice-versa. A flow pathway can include at least one of a hydraulicfracture, and a fluid connection across a screen, across gravel pack,across proppant, including across resin-bonded proppant or proppantdeposited in a fracture, and across sand. A flow pathway can include anatural subterranean passageway through which fluids can flow. In someembodiments, a flow pathway can be a water source and can include water.In some embodiments, a flow pathway can be a petroleum source and caninclude petroleum. In some embodiments, a flow pathway can be sufficientto divert from a wellbore, fracture, or flow pathway connected theretoat least one of water, a downhole fluid, or a produced hydrocarbon.

As used herein, a “carrier fluid” refers to any suitable fluid forsuspending, dissolving, mixing, or emulsifying with one or morematerials to form a composition. For example, the carrier fluid can beat least one of crude oil, dipropylene glycol methyl ether, dipropyleneglycol dimethyl ether, dipropylene glycol methyl ether, dipropyleneglycol dimethyl ether, dimethyl formamide, diethylene glycol methylether, ethylene glycol butyl ether, diethylene glycol butyl ether,butylglycidyl ether, propylene carbonate, D-limonene, a C₂-C₄₀ fattyacid C₁-C₁₀ alkyl ester (e.g., a fatty acid methyl ester),tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, 2-butoxyethanol, butyl acetate, butyl lactate, furfuryl acetate, dimethylsulfoxide, dimethyl formamide, a petroleum distillation product offraction (e.g., diesel, kerosene, napthas, and the like) mineral oil, ahydrocarbon oil, a hydrocarbon including an aromatic carbon-carbon bond(e.g., benzene, toluene), a hydrocarbon including an alpha olefin,xylenes, an ionic liquid, methyl ethyl ketone, an ester of oxalic,maleic or succinic acid, methanol, ethanol, propanol (iso- or normal-),butyl alcohol (iso-, tert-, or normal-), an aliphatic hydrocarbon (e.g.,cyclohexanone, hexane), water, brine, produced water, flowback water,brackish water, and sea water. The fluid can form about 0.001 wt % toabout 99.999 wt % of a composition, or a mixture including the same, orabout 0.001 wt % or less, 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15,20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97,98, 99, 99.9, 99.99, or about 99.999 wt % or more.

In various embodiments, the present invention provides a method oftreating a subterranean formation. The method includes placing in asubterranean formation a composition including a glycerol esterincluding at least two epoxides. The composition also includes ahardening agent.

In various embodiments, the present invention provides a method oftreating a subterranean formation. The method includes placing in asubterranean formation a composition including a glycerol esterincluding at least two epoxides having the structure:

The variables R¹, R², and R³ are independently chosen from—C(O)—(C₂-C₆₀)alkyl and —C(O)—(C₂-C₆₀)alkenyl. In at least one of R¹,R², and R³, the (C₂-C₆₀)alkyl and the (C₂-C₆₀)alkenyl each independentlyinclude about 2 to about 30 oxygen atoms each independently directlybound to two different adjacent carbon atoms of R¹, R², and R³, the(C₂-C₆₀)alkyl and the (C₂-C₆₀)alkenyl (e.g., including 2-30 epoxidegroups). The composition also includes an amine-functional hardeningagent.

In various embodiments, the present invention provides a systemincluding a composition that includes a glycerol ester including atleast two epoxides. The composition also includes a hardening agent. Thesystem also includes a subterranean formation including the compositiontherein.

In various embodiments, the present invention provides a composition fortreatment of a subterranean formation. The composition includes aglycerol ester including at least two epoxides. The composition alsoincludes a hardening agent.

In various embodiments, the present invention provides a method ofpreparing a composition for treatment of a subterranean formation. Themethod includes forming a composition including a glycerol esterincluding at least two epoxides. The composition also includes ahardening agent.

Various embodiments of the present invention provide certain advantagesover other compositions and methods for consolidation, at least some ofwhich are unexpected. In some embodiments, the composition can be moreenvironmentally friendly than other curable compositions. In someembodiments, the epoxide-containing glycerol ester and the hardeningagent can be free of aromatic groups and therefore less toxic than otheraromatic group-containing compositions. In some embodiments, theepoxide-containing glycerol ester can be derived from moreenvironmentally friendly sources than other materials, such as from oilslike vegetable oils. In some embodiments, its greater environmentalfriendliness makes the composition easier to use in areas having strictenvironmental regulations, including, in some examples, use of moreliberal quantities of the composition.

In various embodiments, the composition can be less expensive than otherconsolidating compositions, providing a greater amount of consolidationfor a given cost than other consolidating compositions. In someembodiments, the epoxide-containing glycerol ester can be derived fromcheaper and more renewable resources than other consolidating resins,such as oils like vegetable oils. In various embodiments, thecomposition can cause less damage to the formation than other curablecompositions. In some embodiments, by providing a greater regainpermeability, higher production rates can be achieved.

In various embodiments, the composition can form a stronger bond withproppants, gravel, and subterranean surfaces than other consolidatingcompositions, providing greater strength using a smaller amount ofcurable composition as compared to other treatment methods. In someembodiments, a free hydroxy group can increase bonding strength toparticulate or subterranean surfaces over other curable compositions. Insome embodiments, a more permeable consolidated material can be formedhaving the same or greater strength than a consolidated material formedusing a larger amount of another curable composition. In variousembodiments, by using a smaller amount of curable composition, thecomposition can provide greater regain permeability than otherconsolidating methods that provide similar strength but require largeramounts of resin. In some embodiments, since a smaller amount of curablecomposition is required, a consolidation treatment using the compositioncan proceed more quickly than other consolidation treatments.

Other curable compositions employ a solvent to dilute the compositionand provide lower viscosity, reducing the concentration of the curablematerials and providing reduced consolidating strength. In variousembodiments, the epoxide-containing glycerol ester can act as a reactivediluent, providing reduced viscosity to the uncured composition usingless or no diluting solvent, providing a composition suitable forpumping into subterranean formations having lower permeabilities. Invarious embodiments, the lower viscosity of the composition includingthe epoxide-containing glycerol ester can enable better penetration intothe subterranean formation and can provide better consolidation not onlyin the near wellbore region but also deeper in the formation. In variousembodiments, by acting as a reactive diluent, the epoxide-containingglycerol ester provides dilution and viscosity decrease without reducingthe effective concentration of the epoxide-containing glycerol ester,allowing a high degree of consolidation even in formations with lowerpermeabilities or higher fines content.

In various embodiments, the epoxide-containing glycerol ester can beused in combination with other curable resins, such as other epoxideresins. In various embodiments, the composition including theepoxide-containing glycerol ester can provide good consolidationstrength without decreasing or with only a minor decrease inpermeability of formations that include large amounts of fines andclays. In various embodiments, the composition including theepoxide-containing glycerol ester can have a higher flash point thanother consolidation compositions. In various embodiments, a proppant orgravel coated with a cured reaction product of the epoxide-containingglycerol ester and hardening agent can have enhanced strength and crushresistance compared to a corresponding proppant or gravel that is freeof the coating.

Method of Treating a Subterranean Formation.

In some embodiments, the present invention provides a method of treatinga subterranean formation. The method includes placing in a subterraneanformation a composition including an epoxide-containing glycerol esterand a hardening agent. The composition can be or can include aconsolidating resin. In various embodiments, the composition can be usedin well completion operations, such as primary proppant treatments forimmobilizing proppant particulates (e.g., hydraulic fracturing, gravelpacking, and frac-packing), remedial proppant/gravel treatments,near-wellbore formation sand consolidation treatments for sand control,consolidating-while-drilling target intervals, andplugging-and-abandonment of wellbores in subterranean formations. Insome embodiments, the composition includes the epoxide-containingglycerol ester and hardening agent used as a reactive diluent, such asin a composition including other hardenable resins (e.g., epoxy resinsor other resins) or in a composition only including the glycerol esterand the hardening agent as the hardenable components of the composition.In some embodiments, the composition can include the epoxide-containingglycerol ester and hardening agent or a cured reaction product thereofas a coating on a proppant (e.g., sand) or on gravel. In variousembodiments, a proppant or gravel coated with a cured reaction productof the epoxide-containing glycerol ester and hardening agent can haveenhanced strength and crush resistance compared to a correspondingproppant or gravel that is free of the coating.

The method can include obtaining or providing the composition (e.g.,mixing the epoxide-containing glycerol ester and the hardening agent, ormixing other components to form the composition). The obtaining orproviding of the composition can occur at any suitable time and at anysuitable location. The obtaining or providing of the composition canoccur above the surface. The obtaining or providing of the compositioncan occur in the subterranean formation (e.g., downhole). The methodalso includes placing the composition in a subterranean formation. Theplacing of the composition in the subterranean formation can includecontacting the composition and any suitable part of the subterraneanformation, or contacting the composition and a subterranean material,such as any suitable subterranean material. The subterranean formationcan be any suitable subterranean formation. In some examples, theplacing of the composition in the subterranean formation includescontacting the composition with or placing the composition in at leastone of a fracture, at least a part of an area surrounding a fracture, aflow pathway, an area surrounding a flow pathway, and an area desired tobe fractured. The placing of the composition in the subterraneanformation can be any suitable placing and can include any suitablecontacting between the subterranean formation and the composition. Theplacing of the composition in the subterranean formation can include atleast partially depositing the composition in a fracture, flow pathway,or area surrounding the same.

The method can include hydraulic fracturing, such as a method ofhydraulic fracturing to generate a fracture or flow pathway. The placingof the composition in the subterranean formation or the contacting ofthe subterranean formation and the hydraulic fracturing can occur at anytime with respect to one another; for example, the hydraulic fracturingcan occur at least one of before, during, and after the contacting orplacing. In some embodiments, the contacting or placing occurs duringthe hydraulic fracturing, such as during any suitable stage of thehydraulic fracturing, such as during at least one of a pre-pad stage(e.g., during injection of water with no proppant, and additionallyoptionally mid- to low-strength acid), a pad stage (e.g., duringinjection of fluid only with no proppant, with some viscosifier, such asto begin to break into an area and initiate fractures to producesufficient penetration and width to allow proppant-laden later stages toenter), or a slurry stage of the fracturing (e.g., viscous fluid withproppant). The method can include performing a stimulation treatment atleast one of before, during, and after placing the composition in thesubterranean formation in the fracture, flow pathway, or areasurrounding the same. The stimulation treatment can be, for example, atleast one of perforating, acidizing, injecting of cleaning fluids,propellant stimulation, and hydraulic fracturing. In some embodiments,the stimulation treatment at least partially generates a fracture orflow pathway where the composition is placed or contacted, or thecomposition is placed or contacted to an area surrounding the generatedfracture or flow pathway.

The method can include at least partially curing the composition, toform a cured product of the composition. In some embodiments,substantially all of the composition is curable, while in otherembodiments the composition includes curable components and non-curablecomponents such that only part of the composition is curable. Forexample, in some embodiments, the composition includes a slurry ofproppant particles in a carrier fluid, wherein the proppant particlesare coated with curable components but the carrier fluid issubstantially non-curable. The curable components of the composition canbe a curable resin. In some embodiments, the curable components of thecomposition can be about 0.001 wt % to about 99.999 wt % of thecomposition, or about 0.1 wt % to about 80 wt %, or about 1 wt % toabout 50 wt %, or about 1 wt % or more of the composition, or about 2 wt%, 3, 4, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93,94, 95, 96, 97, 98, 99, 99.9, or about 99.99 wt % or more. In someembodiments, the curing can include curing about 1 wt % or more of thecurable components, or about 2 wt %, 3, 4, 5, 10, 15, 20, 25, 30, 40,50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, orabout 99.99 wt % or more of the curable components of the composition.The curing can occur at any suitable location, such as at the surface,during transport downhole, at a downhole location, or a combinationthereof. In some embodiments, the composition is allowed to react atleast partially above the surface with a gravel or proppant surface toform bonds thereto (e.g., in an embodiment wherein theepoxide-containing glycerol ester includes a free hydroxy group, viahydroxy-reactive silicon groups such as alkoxy- or hydroxy-substitutedsilanes), and the composition is allowed to cure downhole. In someembodiments, reaction with the surface of gravel, proppant, or thesubterranean formation can occur at least partially downhole. The curingcan be initiated by any suitable conditions, such as pressure,temperature, or by presence of a chemical catalyst or initiator. In someembodiments, the composition can include a base, such as any suitableorganic or inorganic base, such as triethylamine, to catalyze the curingprocess.

Any suitable proportion of the composition can be one or more downholefluids or one or more carrier liquids. In some embodiments about 0.001wt % to about 99.999 wt % of the composition can be a downhole fluid orcarrier liquid, or about 0.1 wt % to about 80 wt %, or about 1 wt % toabout 50 wt %, or about 1 wt % or more of the composition, or about 2 wt%, 3, 4, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93,94, 95, 96, 97, 98, 99, 99.9, or about 99.99 wt % or more.

In various embodiments, the composition, a cured product thereof, ormixture including the composition or a cured product thereof can includea proppant or gravel. A proppant is a material that keeps an inducedhydraulic fracture at least partially open during or after a fracturingtreatment. Proppants can be transported into the subterranean formation(e.g., downhole) to the fracture using fluid, such as fracturing fluidor another fluid. A higher-viscosity fluid can more effectivelytransport proppants to a desired location in a fracture, especiallylarger proppants, by more effectively keeping proppants in a suspendedstate within the fluid. Examples of proppants can include sand, gravel,glass beads, polymer beads, ground products from shells and seeds suchas walnut hulls, and manmade materials such as ceramic proppant,bauxite, tetrafluoroethylene materials (e.g., TEFLON™ available fromDuPont), fruit pit materials, processed wood, composite particulatesprepared from a binder and fine grade particulates such as silica,alumina, fumed silica, carbon black, graphite, mica, titanium dioxide,meta-silicate, calcium silicate, kaolin, talc, zirconia, boron, fly ash,hollow glass microspheres, and solid glass, or mixtures thereof. In someembodiments, the proppant can have an average particle size, whereinparticle size is the largest dimension of a particle, of about 0.001 mmto about 3 mm, about 0.15 mm to about 2.5 mm, about 0.25 mm to about0.43 mm, about 0.43 mm to about 0.85 mm, about 0.85 mm to about 1.18 mm,about 1.18 mm to about 1.70 mm, or about 1.70 to about 2.36 mm. In someembodiments, the proppant can have a distribution of particle sizesclustering around multiple averages, such as one, two, three, or fourdifferent average particle sizes. The composition or mixture can includeany suitable amount of proppant or gravel, such as about 0.01 wt % toabout 99.99 wt %, about 1 wt % to about 90 wt %, about 5 wt % to about70 wt %, or about 0.01 wt % or less, or about 0.1 wt %, 1, 2, 3, 4, 5,10, 15, 20, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97,98, 99, about 99.9 wt %, or about 99.99 wt % or more. In someembodiments, the composition includes curable components (e.g., theepoxide-containing glycerol ester and a hardening agent, and any otheroptional curable components) at least partially coated on the proppantor gravel. In some embodiments, the curable components of thecomposition can form or be part of a liquid that suspends the proppantin a slurry.

In various embodiments, the composition includes the epoxide-containingglycerol ester and the hardening agent, a silane coupling agent, asurfactant for facilitating the coating of the curable components onparticulate substrates, and a carrier fluid.

In one embodiment, a method of treating proppant on the fly during thehydraulic fracturing treatment or screenless frac-pack treatment caninclude: mixing components of the composition together to form a single,homogenous mixture; coating the mixture on the proppant while theproppant is being mixed in a fracturing carrier fluid; injecting theresin-treated proppant slurry into a wellbore to be placed in agenerated fracture located in the subterranean formation; allowing thesystem to cure at formation temperature.

In another embodiment, a method of treating the formation with thecomposition includes: mixing components of the composition together in asoluble solvent; injecting the mixture into the formation interval thatrequires treatment; postflushing with a solvent or a gas; allowing thesystem to cure at formation temperature

In one embodiment, the present invention provides a method of treatingproppant using a wet coat or on the fly method, such as during ahydraulic fracturing treatment. In another embodiment, the presentinvention provides a method of dry coating or pretreating the proppantprior to a fracturing treatment, generally including applying a mixtureof the epoxide-containing glycerol ester and the hardening agent, andany other optional components of the composition, to the dry proppant.

The method can further include applying a preflush solution to thesubterranean formation. The preflush solution can be any suitablepreflush solution. For example, the preflush solution can ready thesubterranean material to receive the composition and can remove oilsthat can impede the composition from making contact with particulatesthat are desired to be consolidated by the composition. The preflushsolution can include an aqueous liquid. The aqueous liquid in thepreflush solution can include at least one of salt water and brine. Thepreflush solution can include a surfactant. The surfactant in thepreflush solution can include at least one of an ethoxylated nonylphenol phosphate ester, a cationic surfactant, a non-ionic surfactant,an alkyl phosphonate surfactant, or mixtures thereof.

The method can further include applying an afterflush fluid to thesubterranean formation. For example, the afterflush fluid can displacethe composition from selected areas of the wellbore to remove thecomposition from the pore spaces inside the subterranean formation andthereby restore permeability while leaving behind composition at, forexample, contact points between the subterranean formation andparticulates such that the particulates can be consolidated. Theafterflush fluid can be any suitable afterflush fluid, such as at leastone of salt water, brine, and nitrogen gas.

Epoxide-Containing Glycerol Ester.

The composition includes a glycerol ester that includes at least twoepoxide groups. The composition can include one or more glycerol estersthat include at least two epoxide groups. The epoxide-containingglycerol ester can be present in the composition in any suitableconcentration, such that the composition can be used as describedherein. For example, the one or more epoxide-containing glycerol esterscan be about 0.001 wt % to about 50 wt % of the composition, about 0.01wt % to about 30 wt % of the composition, about 0.001 wt % or less,about 0.005 wt %, 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5,5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 35, 40, 45,or about 50 wt % or more of the composition.

The epoxide-containing glycerol ester can be any suitable ester ofglycerol. The glycerol ester can be at least one of a mono-, di-, ortri-glyceride (e.g., having two, one, or zero free hydroxy groups on theglycerol, respectively). The glycerol esters can be fatty acid (e.g.,C₅-C₆₀) glycerol esters.

In some embodiments, the glycerol ester including at least two epoxideshas the following structure:

The variables R¹, R², and R³ can be independently chosen from —H,substituted or unsubstituted (C₁-C₆₀)hydrocarbyl, and R⁴. The variableR⁴ at each occurrence can be independently —C(O)—(C₂-C₆₀)hydrocarbylincluding at least two oxygen atoms each independently directly attachedto two different adjacent carbon atoms of the (C₂-C₆₀)hydrocarbyl. The(C₁-C₆₀)hydrocarbyl and the (C₂-C₆₀)hydrocarbyl can be independentlyinterrupted by 0, 1, 2, or 3 groups independently chosen from —O—, —S—,and substituted or unsubstituted —NH—. At least one of R¹, R², and R³can be R⁴.

The variables R¹, R², and R³ can be independently chosen from —H,substituted or unsubstituted (C₁-C₆₀)hydrocarbyl, and R⁴. In someembodiments, each of R¹, R², and R³ are independently selected from R⁴and —H. In some embodiments, at least two of R¹, R², and R³ are R⁴. Insome embodiments, each of R¹, R², and R³ is R⁴. In some embodiments, R¹,R², and R³ are independently chosen from —H, substituted orunsubstituted (C₅-C₆₀)alkyl, substituted or unsubstituted—C(O)—(C₄-C₅₉)alkyl substituted or unsubstituted (C₅-C₆₀)alkenyl,substituted or unsubstituted —C(O)—(C₄-C₅₉)alkenyl, and R⁴. The(C₅-C₆₀)alkenyl and the —C(O)—(C₄-C₅₉)alkenyl can each independentlyinclude about 1 to about 29 carbon-carbon double bonds (e.g., 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,23, 24, 25, 26, 27, 28, or 29). The (C₅-C₆₀)alkyl, the—C(O)—(C₄-C₅₉)alkyl, the (C₅-C₆₀)alkenyl, and the —C(O)—(C₄-C₅₉)alkenylcan each independently include about 2 to about 30 oxygen atoms eachindependently directly bound to two different adjacent carbon atoms ofthe (C₅-C₆₀)alkyl, the —C(O)—(C₄-C₅₉)alkyl, the (C₅-C₆₀)alkenyl, and the—C(O)—(C₄-C₅₉)alkenyl (e.g., including 2-30 epoxide groups). In someembodiments, R⁴ at each occurrence is independently chosen from—C(O)—(C₂-C₆₀)alkyl and —C(O)—(C₂-C₆₀)alkenyl. The (C₂-C₆₀)alkyl and the(C₂-C₆₀)alkenyl can each independently include about 2 to about 30oxygen atoms each independently directly bound to two different adjacentcarbon atoms of the (C₂-C₆₀)alkyl or the (C₂-C₆₀)alkenyl (e.g., 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,23, 24, 25, 26, 27, 28, 29, or 30 epoxide groups). As used herein“adjacent carbon atoms” are carbon atoms that are directly bound to oneanother.

In some embodiments, the glycerol ester including at least two epoxidesis an oil including at least one epoxidized aliphatic carbon-carbondouble bond. For example, the glycerol ester including at least twoepoxides can be an oil that has been epoxidized (e.g., wherein at leastone aliphatic carbon-carbon double bond has been epoxidized). The oilcan be açai oil, almond oil, amaranth oil, apple seed oil, apricot oil,argan oil, avocado oil, babassu oil, beech nut oil, ben oil, bittergourd oil (from the seeds of Momordica charantia), black seed oil,blackcurrant seed oil (from the seeds of Ribes nigrum), borage seed oil(from the seeds of Borago officinalis), borneo tallow nut oil, bottlegourd oil (from the seeds of the Lagenaria siceraria), buffalo gourd oil(from the seeds of the Cucurbita foetidissima), butternut squash seedoil (from the seeds of Cucurbita moschata), camelina sativa oil, capechestnut oil (yangu oil), carob pod oil, cashew oil, cocklebur oil,cocoa butter, coconut oil, cohune oil, coriander seed oil, corn oil,cottonseed oil, date seed oil, dika oil, egusi seed oil (from the seedsof Cucumeropsis mannii naudin), evening primrose oil (from the seeds ofOenothera biennis), flaxseed oil (from the seeds of Linumusitatissimum), grape seed oil, grapefruit seed oil, hazelnut oil, hempoil, kapok seed oil, kenaf seed oil (from the seeds of Hibiscuscannabinus), lallemantia oil (from the seeds of Lallemantia iberica),linseed oil, macadamia oil, mafura oil (from the seeds of Trichiliaemetic), manila oil (from the kernel of Sclerocarya birrea), meadowfoamseed oil, mongongo nut oil (manketti oil), mustard oil, niger seed oil,okra seed oil, olive oil, orange oil, palm oil, papaya seed oil, peanutoil, pecan oil, pequi oil (from the seeds of Caryocar brasiliense),perilla seed oil, persimmon seed oil (from the seeds of Diospyrosvirginiana), pili nut oil (from the seeds of Canarium ovatum), pistachiooil, pomegranate seed oil, poppyseed oil, prune kernel oil, pumpkin seedoil, quinoa oil, ramtil oil (from Guizotia abyssinica, the Niger pea),rapeseed oil, rice bran oil, royle oil (from the seeds of Prinsepiautilis), safflower oil, sapote oil, seje oil (from the seeds of Jesseniabataua), sesame oil, shea butter, soybean oil, sunflower oil, taramiraoil, tea seed oil (Camellia oil), thistle oil, tigernut oil (ornut-sedge oil), tobacco seed oil, tomato seed oil, walnut oil,watermelon seed oil, wheat germ oil, one or more fractions thereof(e.g., one or more components of the oil), or a combination thereof Insome embodiments, the oil can be chosen from agarwood oil, allspice oil,almond oil, anise oil, basil oil, bay leaf oil, benzoin oil, bergamotoil, buchu oil, camphor oil, cannabis oil, cassia oil, cedar oil, celeryoil, chamomile oil, cinnamon oil, clary sage oil, clove oil, copaibaoil, cumin oil, eucalyptus oil, frankincense oil, galangal oil, geraniumoil, ginger oil, grapefruit oil, guava oil, hops oil, hyssop oil,jasmine oil, juniper oil, lavender oil, lemon grass oil, lemon oil,lemongrass oil, lime oil, manuka oil, mandarin orange, marjoram oil,melaleuca oil, myrrh oil, nutmeg oil, orange oil, oregano oil, patchoulioil, peppermint oil, pine oil, rose oil, rosehip oil, rosemary oil,rosewood oil, sage oil, sandalwood oil, sassafras oil, spearmint oil,tangerine oil, tea tree oil, thyme oil, tsuga oil, valerian oil, vanillaoil, wintergreen oil, ylang-ylang oil, one or more fractions thereof(e.g., one or more components of the oil), or a combination thereof Insome embodiments, the oil can be chosen from soybean oil, linseed oil, afraction thereof, and combinations thereof.

In some embodiments, the glycerol ester including at least two epoxidescan have the structure:

In some embodiments, the glycerol ester including at least two epoxidescan have the structure:

The glycerol ester including at least two epoxides can have any suitableepoxide equivalent weight (e.g., the grams of the glycerol ester neededto provide 1 mole of epoxide functionalities) consistent with thestructures described herein. For example, the epoxide-containingglycerol ester can have an epoxide equivalent weight of about 50 g/molto about 1,000 g/mol, or about 100 g/mol to about 500 g/mol, or about150 g/mol to about 300 g/mol, or about 50 g/mol or less, or about 75g/mol, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400,425, 450, 475, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, orabout 1,000 g/mol or more.

Hardening Agent.

The hardening agent can be any suitable hardening agent that can reactwith the epoxide-containing glycerol ester to form a cured productthereof that is effective for consolidation. The hardening agent can bean epoxide-reactive hardening agent. The hardening agent can include anucleophilic group that can attack and open an epoxide, such as aprimary or secondary amine. The hardening agent can be anamine-functional hardening agent, and can include at least one of anamine, an aromatic amine, an aliphatic amine, a cyclo-aliphatic amine, apolyamine, an amide, and a polyamide. The hardening agent can beselected from the group consisting of diethylene tetramine, ethylenediamine, polyethyleneimine, piperidine, triethylamine,benzyldimethylamine, N,N-dimethylaminopyridine,2-(N,N-dimethylaminomethyl)phenol, tris(dimethylaminomethyl)phenol,N-2-(aminoethyl)-3-aminopropyltrimethoxysilane,3-glycidoxypropyltrimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane, piperazine, aminoethylpiperazine, pyrrole, imidazole,pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine,isoindole, indole, indazole, purine, quinolizine, quinoline,isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline,carbazole, carbazole, phenanthridine, acridine, phenathroline,phenazine, imidazolidine, phenoxazine, cinnoline, pyrrolidine,pyrroline, imidazoline, piperidine, indoline, isoindoline,quinuclindine, morpholine, azocine, azepine, azepine, 1,3,5-triazine,thiazole, pteridine, dihydroquinoline, hexamethyleneimine, indazole,polyethyleneimine, 2-ethyl-4-methyl imidazole,1,1,3-trichlorotrifluoroacetone, a substituted or unsubstitutedderivative of any one thereof, and combinations thereof.

In some embodiments, the hardening agent can include an amine-containingpolymer. In some embodiments, the hardening agent can behydrophobically-modified. In some embodiments, the hardening agent caninclude at least one of a polyamine (e.g., spermidine and spermine), apolyimine (e.g., poly(ethylene imine) and poly(propylene imine)), apolyamide, poly(2-(N,N-dimethylamino)ethyl methacrylate),poly(2-(N,N-diethylamino)ethyl methacrylate), poly(vinyl imidazole), anda copolymer including monomers of at least one of the foregoing andmonomers of at least one non-amine-containing polymer such as of atleast one of polyethylene, polypropylene, polyethylene oxide,polypropylene oxide, polyvinylpyridine, polyacrylic acid, polyacrylate,and polymethacrylate. The hydrophobic modification can be any suitablehydrophobic modification, such as at least one (C₄-C₃₀)hydrocarbylincluding at least one of a straight chain, a branched chain, anunsaturated C—C bond, an aryl group, and any combination thereof.

The hardening agent can include at least one amine component that is apolyamine-substituted (C₁-C₃₀)hydrocarbyl, whererein the(C₁-C₃₀)hydrocarbyl and each amine are independently substituted orunsubstituted, in any suitable proportion of the composition, such asabout 5 wt % to about 50 wt %, about 10 wt % to about 30 wt %, about 5wt % or less, or about 10 wt %, 15, 20, 25, 30, 35, 40, 45, or about 50wt % or more. The hardening agent can be abis(amino(C₀-C₅)hydrocarbyl)(C₆-C₂₀)aryl compound, wherein the(C₆-C₂₀)aryl, (C₀-C₅)hydrocarbyl, and each amine are each independentlysubstituted or unsubstituted. The amine component can bediethyltoluenediamine. The hardening agent can include at least oneamine component that is a polyamine-substitutedpoly((C₂-C₅)hydrocarbyloxy), wherein each (C₂-C₅)hydrocarbyloxy and eachamine are independently substituted or unsubstituted. The hardeningagent can be polyoxypropylene diamine. The hardening agent can includean amine component that is a mono- orpolyamino(C₀-C₁₀)hydrocarbyl(C₆-C₂₀)aryl compound, wherein the(C₀-C₁₀)hydrocarbyl, (C₆-C₂₀)aryl, and each amine are each independentlysubstituted or unsubstituted. The hardening agent can be atris(amino(C₁-C₃)hydrocarbyl)benzene, wherein the (C₁-C₃)hydrocarbyl,the benzene, and each amine are independently substituted orunsubstituted. The amine component can be2,4,6-tris(dimethylaminomethyl)phenol.

Other Components.

The composition including the epoxide-containing glycerol ester and thehardening agent, a mixture including the composition, or a cured productthereof, can include any suitable additional component in any suitableproportion, such that the composition, mixture including the same, orcured product thereof, can be used as described herein.

In some embodiments, the composition or a cured product thereof furtherincludes a silane coupling agent. The silane coupling agent can be anysuitable silane coupling agent. For example, the silane coupling agentcan be a (C₁-C₃₀)hydrocarbyl-substituted trimethoxysilane, wherein thehydrocarbyl group is substituted or unsubstituted. The silane couplingagent can be N-2-(aminoethyl)-3-aminopropyltrimethoxysilane,3-glycidoxypropyltrimethoxysilane, orn-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane. Any suitableamount of the composition or a cured product thereof can be the silanecoupling agent, such as about 0.001 wt % to about 20 wt %, or about0.001 wt % to about 3 wt %, or about 0.001 wt % or less, or about 0.01,0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, or about 20 wt % or more.

The composition or a cured product thereof can include one or moresurfactants. The surfactant can facilitate the coating of the curablecomponents of the composition on proppant, gravel, or a subterraneansurface causing the curable components to flow to the contact pointsbetween adjacent proppant particles. The surfactant can be any suitablesurfactant, such that the composition can be used as described herein.The surfactant can form any suitable proportion of the composition or acured product thereof, such that the composition or cured productthereof can be used as described herein. For example, about 0.0001 wt %to about 20 wt % of the composition or cured product thereof can be theone or more surfactants, about 0.001 wt % to about 1 wt %, or about0.0001 wt % or less, or about 0.001 wt %, 0.005, 0.01, 0.02, 0.04, 0.06,0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,11, 12, 13, 14, 15, 16, 17, 18, 19, or about 20 wt % or more.

In some embodiments, the surfactant is at least one of a cationicsurfactant, an anionic surfactant, and a non-ionic surfactant. In someembodiments, the ionic groups of the surfactant can include counterions,such that the overall charge of the ionic groups is neutral, whereas inother embodiments, no counterion can be present for one or more ionicgroups, such that the overall charge of the one or more ionic groups isnot neutral.

In one example, the surfactant can be a non-ionic surfactant. Examplesof non-ionic surfactants can include polyoxyethylene alkyl ethers,polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers,polyoxyethylene sorbitan monoleates, polyoxyethylene alkyl esters,polyoxyethylene sorbitan alkyl esters, polyethylene glycol,polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanols,polyoxyalkylene glycol modified polysiloxane surfactants, and mixtures,copolymers or reaction products thereof. In one example, the surfactantis polyglycol-modified trimethylsilylated silicate surfactant. Examplesof suitable non-ionic surfactants can include, but are not limited to,condensates of ethylene oxide with long chain fatty alcohols or fattyacids such as a (C₁₂₋₁₆)alcohol, condensates of ethylene oxide with anamine or an amide, condensation products of ethylene and propyleneoxide, esters of glycerol, sucrose, sorbitol, fatty acid alkylol amides,sucrose esters, fluoro-surfactants, fatty amine oxides, polyoxyalkylenealkyl ethers such as polyethylene glycol long chain alkyl ether,polyoxyalkylene sorbitan ethers, polyoxyalkylene alkoxylate esters,polyoxyalkylene alkylphenol ethers, ethylene glycol propylene glycolcopolymers and alkylpolysaccharides, polymeric surfactants such aspolyvinyl alcohol (PVA) and polyvinylmethylether. In certainembodiments, the surfactant is a polyoxyethylene fatty alcohol ormixture of polyoxyethylene fatty alcohols. In other embodiments, thesurfactant is an aqueous dispersion of a polyoxyethylene fatty alcoholor mixture of polyoxyethylene fatty alcohols. In some examples, suitablenon-ionic surfactants can include at least one of an alkylpolyglycoside, a sorbitan ester, a methyl glucoside ester, an amineethoxylate, a diamine ethoxylate, a polyglycerol ester, an alkylethoxylate, an alcohol that has been at least one of polypropoxylatedand polyethoxylated, any derivative thereof, or any combination thereof.

Examples of suitable anionic surfactants can include, but are notlimited to, alkyl sulphates such as lauryl sulphate, polymers such asacrylates/C₁₀₋₃₀ alkyl acrylate crosspolymer alkylbenzenesulfonic acidsand salts such as hexylbenzenesulfonic acid, octylbenzenesulfonic acid,decylbenzenesulfonic acid, dodecylbenzenesulfonic acid,cetylbenzenesulfonic acid and myristylbenzenesulfonic acid; the sulphateesters of monoalkyl polyoxyethylene ethers; alkylnapthylsulfonic acid;alkali metal sulfoccinates, sulfonated glyceryl esters of fatty acidssuch as sulfonated monoglycerides of coconut oil acids, salts ofsulfonated monovalent alcohol esters, amides of amino sulfonic acids,sulfonated products of fatty acid nitriles, sulfonated aromatichydrocarbons, condensation products of naphthalene sulfonic acids withformaldehyde, sodium octahydroanthracene sulfonate, alkali metal alkylsulphates, ester sulphates, and alkarylsulfonates. Anionic surfactantscan include alkali metal soaps of higher fatty acids, alkylarylsulfonates such as sodium dodecyl benzene sulfonate, long chain fattyalcohol sulfates, olefin sulfates and olefin sulfonates, sulfatedmonoglycerides, sulfated esters, sulfonated ethoxylated alcohols,sulfosuccinates, alkane sulfonates, phosphate esters, alkylisethionates, alkyl taurates, and alkyl sarcosinates.

Suitable cationic surfactants can include at least one of an argininemethyl ester, an alkanolamine, an alkylenediamide, an alkyl estersulfonate, an alkyl ether sulfonate, an alkyl ether sulfate, an alkalimetal alkyl sulfate, an alkyl or alkylaryl sulfonate, a sulfosuccinate,an alkyl or alkylaryl disulfonate, an alkyl disulfate, an alcoholpolypropoxylated or polyethoxylated sulfates, a taurate, an amine oxide,an alkylamine oxide, an ethoxylated amide, an alkoxylated fatty acid, analkoxylated alcohol, an ethoxylated fatty amine, an ethoxylated alkylamine, a betaine, a modified betaine, an alkylamidobetaine, a quaternaryammonium compound, any derivative thereof, and any combination thereof.Examples of suitable cationic surfactants can include quaternaryammonium hydroxides such as octyl trimethyl ammonium hydroxide, dodecyltrimethyl ammonium hydroxide, hexadecyl trimethyl ammonium hydroxide,octyl dimethyl benzyl ammonium hydroxide, decyl dimethyl benzyl ammoniumhydroxide, didodecyl dimethyl ammonium hydroxide, dioctadecyl dimethylammonium hydroxide, tallow trimethyl ammonium hydroxide and cocotrimethyl ammonium hydroxide as well as corresponding salts of thesematerials, fatty amines and fatty acid amides and their derivatives,basic pyridinium compounds, and quaternary ammonium bases ofbenzimidazolines and poly(ethoxylated/propoxylated) amines.

In some embodiments, the surfactant can be selected from Tergitol™15-s-3, Tergitol™ 15-s-40, sorbitan monooleate, polyglycol-modifiedtrimethsilylated silicate, polyglycol-modified siloxanes,polyglycol-modified silicas, ethoxylated quaternary ammonium saltsolutions, cetyltrimethylammonium chloride or bromide solutions, anethoxylated nonyl phenol phosphate ester, and a (C₁₂-C₂₂)alkylphosphonate. In some examples, the surfactant can be a sulfonate methylester, a hydrolyzed keratin, a polyoxyethylene sorbitan monopalmitate, apolyoxyethylene sorbitan monostearate, a polyoxyethylene sorbitanmonooleate, a linear alcohol alkoxylate, an alkyl ether sulfate,dodecylbenzene sulfonic acid, a linear nonyl-phenol, dioxane, ethyleneoxide, polyethylene glycol, an ethoxylated castor oil,dipalmitoyl-phosphatidylcholine, sodium 4-(1′heptylnonyl)benzenesulfonate, polyoxyethylene nonyl phenyl ether, sodiumdioctyl sulphosuccinate, tetraethyleneglycoldodecylether, sodiumoctlylbenzenesulfonate, sodium hexadecyl sulfate, sodium laurethsulfate, decylamine oxide, dodecylamine betaine, dodecylamine oxide,N,N,N-trimethyl-1-octadecammonium chloride, xylenesulfonate and saltsthereof (e.g., sodium xylene sulfonate), sodium dodecyl sulfate,cetyltrimethylammonium bromide, any derivative thereof, or anycombination thereof The surfactant can be at least one of alkylpropoxy-ethoxysulfonate, alkyl propoxy-ethoxysulfate,alkylaryl-propoxy-ethoxysulfonate, a mixture of an ammonium salt of analkyl ether sulfate, cocoamidopropyl betaine, cocoamidopropyldimethylamine oxide, an ethoxylated alcohol ether sulfate, an alkyl oralkene amidopropyl betaine, an alkyl or alkene dimethylamine oxide, analpha-olefinic sulfonate surfactant, any derivative thereof, and anycombination thereof Suitable surfactants may also include polymericsurfactants, block copolymer surfactants, di-block polymer surfactants,hydrophobically modified surfactants, fluoro-surfactants, andsurfactants containing a non-ionic spacer-arm central extension and anionic or nonionic polar group. In some examples, the non-ionicspacer-arm central extension can be the result of at least one ofpolypropoxylation and polyethoxylation.

In various embodiments, the surfactant is at least one of a substitutedor unsubstituted (C₅-C₅₀)hydrocarbylsulfate salt, a substituted orunsubstituted (C₅-C₅₀)hydrocarbylsulfate (C₁-C₂₀)hydrocarbyl esterwherein the (C₁-C₂₀)hydrocarbyl is substituted or unsubstituted, and asubstituted or unsubstituted (C₅-C₅₀)hydrocarbylbisulfate. Thesurfactant can be at least one of a (C₅-C₂₀)alkylsulfate salt, a(C₅-C₂₀)alkylsulfate (C₁-C₂₀)alkyl ester and a (C₅-C₂₀)alkylbisulfate.In various embodiments the surfactant is a (C₈-C₁₅)alkylsulfate salt,wherein the counterion can be any suitable counterion, such as Na⁺, K⁺,Li⁺, H⁺, Zn⁺, NH₄ ⁺, Ca²⁺, Mg²⁺, Zn²⁺, or Al³⁺. In some embodiments, thesurfactant is a (C₈-C₁₅)alkylsulfate salt sodium salt. In someembodiments, the surfactant is sodium dodecyl sulfate.

In various embodiments, the surfactant is a(C₅-C₅₀)hydrocarbyltri((C₁-C₅₀)hydrocarbyl)ammonium salt, wherein each(C₅-C₅₀)hydrocarbyl is independently selected. The counterion can be anysuitable counterion, such as Na⁺, K⁺, Li⁺, H⁺, Zn⁺, NH₄ ⁺, Ca²⁻, Mg²⁺,Zn²⁺, or Al³⁺. The surfactant can be a(C₅-C₅₀)alkyltri((C₁-C₂₀)alkyl)ammonium salt, wherein each (C₅-C₅₀)alkylis independently selected. The surfactant can be a(C₁₀-C₃₀)alkyltri((C₁-C₁₀)alkyl)ammonium halide salt, wherein each(C₁₀-C₃₀)alkyl is independently selected. The surfactant can becetyltrimethylammonium bromide.

In some embodiments, the composition or a cured product thereof canfurther include a hydrolyzable ester. The hydrolyzable ester can be anysuitable hydrolyzable ester. For example, the hydrolyzable ester can bea C₁-C₅ mono-, di-, tri-, or tetra-alkyl ester of a C₂-C₄₀ mono-, di-,tri-, or tetra-carboxylic acid. The hydrolyzable ester can be at leastone of dimethylglutarate, dimethyladipate, dimethylsuccinate, sorbitol,catechol, dimethylthiolate, methyl salicylate, dimethylsalicylate, andtert-butylhydroperoxide. Any suitable wt % of the composition or a curedproduct thereof can be the hydrolyzable ester, such as about 0.01 wt %to about 20 wt %, or about 0.1 wt % to about 5 wt %, or about 0.01 wt %or less, or about 0.1 wt %, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, orabout 20 wt % or more.

In some embodiments, the composition or a cured product thereof furtherincludes at least one tackifier. The tackifier can be any suitable wt %of the composition or cured product thereof, such as about 0.001 wt % toabout 50 wt %, about 0.01 wt % to about 30 wt %, or about 0.001 wt % orless, or about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35,40, 45, or about 50 wt % or more. The tackifier can be any suitablematerial having tackiness. For example, the tackifier can be an adhesiveor a resin. The term “resin” as used herein refers to any of numerousphysically similar polymerized synthetics or chemically modified naturalresins including thermoplastic materials and thermosetting materials. Insome embodiments, the tackifier can be at least one of a shellac, apolyamide, a silyl-modified polyamide, a polyester, a polycarbonate, apolycarbamate, a urethane, a natural resin, an epoxy-based resin, afuran-based resin, a phenolic-based resin, a urea-aldehyde resin, and aphenol/phenol formaldehyde/furfuryl alcohol resin. In some embodiments,the tackifier can be at least one of bisphenol A diglycidyl ether resin,butoxymethyl butyl glycidyl ether resin, bisphenol A-epichlorohydrinresin, and bisphenol F resin. In some embodiments, the tackifier can beat least one of an acrylic acid polymer, an acrylic acid ester polymer,an acrylic acid homopolymer, an acrylic acid ester homopolymer,poly(methyl acrylate), poly(butyl acrylate), poly(2-ethylhexylacrylate), an acrylic acid ester copolymer, a methacrylic acidderivative polymer, a methacrylic acid homopolymer, a methacrylic acidester homopolymer, poly(methyl methacrylate), poly(butyl methacrylate),poly(2-ethylhexyl methacrylate), an acrylamidomethylpropane sulfonatepolymer or copolymer or derivative thereof, and an acrylicacid/acrylamidomethylpropane sulfonate copolymer. In some embodiments,the tackifier can include at least one of a trimer acid, a fatty acid, afatty acid-derivative, maleic anhydride, acrylic acid, a polyester, apolycarbonate, a polycarbamate, an aldehyde, formaldehyde, a dialdehyde,glutaraldehyde, a hemiacetal, an aldehyde-releasing compound, a diacidhalide, a dihalide, a dichloride, a dibromide, a polyacid anhydride,citric acid, an epoxide, furfuraldehyde, an aldehyde condensate, asilyl-modified polyamide, and a condensation reaction product of apolyacid and a polyamine.

In some embodiments, the tackifier can include an amine-containingpolymer. In some embodiments, the tackifier can behydrophobically-modified. In some embodiments, the tackifier can includeat least one of a polyamine (e.g., spermidine and spermine), a polyimine(e.g., poly(ethylene imine) and poly(propylene imine)), a polyamide,poly(2-(N,N-dimethylamino)ethyl methacrylate),poly(2-(N,N-diethylamino)ethyl methacrylate), poly(vinyl imidazole), anda copolymer including monomers of at least one of the foregoing andmonomers of at least one non-amine-containing polymer such as of atleast one of polyethylene, polypropylene, polyethylene oxide,polypropylene oxide, polyvinylpyridine, polyacrylic acid, polyacrylate,and polymethacrylate. The hydrophobic modification can be any suitablehydrophobic modification, such as at least one C₄-C₃₀ hydrocarbylincluding at least one of a straight chain, a branched chain, anunsaturated C—C bond, an aryl group, and any combination thereof.

In some embodiments, the composition or a cured product thereof caninclude a curing agent. The second curing agent can be any suitablecuring agent. For example, the curing agent can include at least one ofan amine, an aromatic amine, an aliphatic amine, a cyclo-aliphaticamine, polyamines, amides, polyamides, piperidine, diethylene tetramine,ethylene diamine, triethylamine, benzyldimethylamine,N,N-dimethylaminopyridine, 2-(N,N-dimethylaminomethyl)phenol,tris(dimethylaminomethyl)phenol,N-2-(aminoethyl)-3-aminopropyltrimethoxysilane,3-glycidoxypropyltrimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane, piperazine, derivatives of piperazine (e.g.,aminoethylpiperazine), pyrrole, imidazole, pyrazole, pyridine, pyrazine,pyrimidine, pyridazine, indolizine, isoindole, indole, indazole, purine,quinolizine, quinoline, isoquinoline, phthalazine, naphthyridine,quinoxaline, quinazoline, carbazole, carbazole, phenanthridine,acridine, phenathroline, phenazine, imidazolidine, phenoxazine,cinnoline, pyrrolidine, pyrroline, imidazoline, piperidine, indoline,isoindoline, quinuclindine, morpholine, azocine, azepine, azepine,1,3,5-triazine, thiazole, pteridine, dihydroquinoline, hexa methyleneimine, indazole, polyamines, amides, polyamides, 2-ethyl-4-methylimidazole, 1,1,3-trichlorotrifluoroacetone, and combinations thereof.The curing agent can form any suitable wt % of the composition or acured product thereof, such as about 0.001 wt % to about 50 wt %, about0.01 wt % to about 20 wt %, or about 0.001 wt % or less, or about 0.01wt %, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, or about 50 wt % ormore.

In some embodiments, the composition or cured product thereof includesone or more viscosifiers. The viscosifier can be any suitableviscosifier. The viscosifier can affect the viscosity of thecomposition, cured product thereof, or a solvent that contacts thecomposition or cured product thereof at any suitable time and location.In some embodiments, the viscosifier provides an increased viscosity atleast one of before injection into the subterranean formation, at thetime of injection into the subterranean formation, during travel througha tubular disposed in a borehole, once the composition reaches aparticular subterranean location, or some period of time after thecomposition reaches a particular subterranean location. In someembodiments, the viscosifier can be about 0.000,1 wt % to about 10 wt %of the composition or a cured product thereof, about 0.004 wt % to about0.01 wt %, or about 0.000,1 wt % or less, 0.000,5 wt %, 0.001, 0.005,0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or about 10 wt % ormore.

The viscosifier can include at least one of a substituted orunsubstituted polysaccharide, and a substituted or unsubstitutedpolyalkene (e.g., a polyethylene, wherein the ethylene unit issubstituted or unsubstituted, derived from the corresponding substitutedor unsubstituted ethene), wherein the polysaccharide or polyalkene iscrosslinked or uncrosslinked. The viscosifier can include a polymerincluding at least one monomer selected from the group consisting ofethylene glycol, acrylamide, vinyl acetate, 2-acrylamidomethylpropanesulfonic acid or its salts, trimethylammoniumethyl acrylate halide, andtrimethylammoniumethyl methacrylate halide. The viscosifier can includea crosslinked gel or a crosslinkable gel. The viscosifier can include atleast one of a linear polysaccharide, and a poly((C₂-C₁₀)alkene),wherein the (C₂-C₁₀)alkene is substituted or unsubstituted. Theviscosifier can include at least one of poly(acrylic acid) or(C₁-C₅)alkyl esters thereof, poly(methacrylic acid) or (C₁-C₅)alkylesters thereof, poly(vinyl acetate), poly(vinyl alcohol), poly(ethyleneglycol), poly(vinyl pyrrolidone), polyacrylamide, poly (hydroxyethylmethacrylate), alginate, chitosan, curdlan, dextran, emulsan, agalactoglucopolysaccharide, gellan, glucuronan, N-acetyl-glucosamine,N-acetyl-heparosan, hyaluronic acid, kefiran, lentinan, levan, mauran,pullulan, scleroglucan, schizophyllan, stewartan, succinoglycan,xanthan, welan, derivatized starch, tamarind, tragacanth, guar gum,derivatized guar (e.g., hydroxypropyl guar, carboxy methyl guar, orcarboxymethyl hydroxypropyl guar), gum ghatti, gum arabic, locust beangum, and derivatized cellulose (e.g., carboxymethyl cellulose,hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose,hydroxypropyl cellulose, or methyl hydroxy ethyl cellulose).

In some embodiments, the viscosifier can include at least one of apoly(vinyl alcohol) homopolymer, poly(vinyl alcohol) copolymer, acrosslinked poly(vinyl alcohol) homopolymer, and a crosslinkedpoly(vinyl alcohol) copolymer. The viscosifier can include a poly(vinylalcohol) copolymer or a crosslinked poly(vinyl alcohol) copolymerincluding at least one of a graft, linear, branched, block, and randomcopolymer of vinyl alcohol and at least one of a substituted orunsubstitued (C₂-C₅₀)hydrocarbyl having at least one aliphaticunsaturated C—C bond therein, and a substituted or unsubstituted(C₂-C₅₀)alkene. The viscosifier can include a poly(vinyl alcohol)copolymer or a crosslinked poly(vinyl alcohol) copolymer including atleast one of a graft, linear, branched, block, and random copolymer ofvinyl alcohol and at least one of vinyl phosphonic acid, vinylidenediphosphonic acid, substituted or unsubstituted2-acrylamido-2-methylpropanesulfonic acid, a substituted orunsubstituted (C₁-C₂₀)alkenoic acid, propenoic acid, butenoic acid,pentenoic acid, hexenoic acid, octenoic acid, nonenoic acid, decenoicacid, acrylic acid, methacrylic acid, hydroxypropyl acrylic acid,acrylamide, fumaric acid, methacrylic acid, hydroxypropyl acrylic acid,vinyl phosphonic acid, vinylidene diphosphonic acid, itaconic acid,crotonic acid, mesoconic acid, citraconic acid, styrene sulfonic acid,allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, and asubstituted or unsubstituted (C₁-C₂₀)alkyl ester thereof. Theviscosifier can include a poly(vinyl alcohol) copolymer or a crosslinkedpoly(vinyl alcohol) copolymer including at least one of a graft, linear,branched, block, and random copolymer of vinyl alcohol and at least oneof vinyl acetate, vinyl propanoate, vinyl butanoate, vinyl pentanoate,vinyl hexanoate, vinyl 2-methyl butanoate, vinyl 3-ethylpentanoate, andvinyl 3-ethylhexanoate, maleic anhydride, a substituted or unsubstituted(C₁-C₂₀)alkenoic substituted or unsubstituted (C₁-C₂₀)alkanoicanhydride, a substituted or unsubstituted (C₁-C₂₀)alkenoic substitutedor unsubstituted (C₁-C₂₀)alkenoic anhydride, propenoic acid anhydride,butenoic acid anhydride, pentenoic acid anhydride, hexenoic acidanhydride, octenoic acid anhydride, nonenoic acid anhydride, decenoicacid anhydride, acrylic acid anhydride, fumaric acid anhydride,methacrylic acid anhydride, hydroxypropyl acrylic acid anhydride, vinylphosphonic acid anhydride, vinylidene diphosphonic acid anhydride,itaconic acid anhydride, crotonic acid anhydride, mesoconic acidanhydride, citraconic acid anhydride, styrene sulfonic acid anhydride,allyl sulfonic acid anhydride, methallyl sulfonic acid anhydride, vinylsulfonic acid anhydride, and an N—(C₁-C₁₀)alkenyl nitrogen containingsubstituted or unsubstituted (C₁-C₁₀)heterocycle. The viscosifier caninclude a poly(vinyl alcohol) copolymer or a crosslinked poly(vinylalcohol) copolymer including at least one of a graft, linear, branched,block, and random copolymer that includes apoly(vinylalcohol/acrylamide) copolymer, apoly(vinylalcohol/2-acrylamido-2-methylpropanesulfonic acid) copolymer,a poly (acrylamide/2-acrylamido-2-methylpropanesulfonic acid) copolymer,or a poly(vinylalcohol/N-vinylpyrrolidone) copolymer. The viscosifiercan include a crosslinked poly(vinyl alcohol) homopolymer or copolymerincluding a crosslinker including at least one of chromium, aluminum,antimony, zirconium, titanium, calcium, boron, iron, silicon, copper,zinc, magnesium, and an ion thereof. The viscosifier can include acrosslinked poly(vinyl alcohol) homopolymer or copolymer including acrosslinker including at least one of an aldehyde, an aldehyde-formingcompound, a carboxylic acid or an ester thereof, a sulfonic acid or anester thereof, a phosphonic acid or an ester thereof, an acid anhydride,and an epihalohydrin.

In various embodiments, the composition or a cured product thereof caninclude one or more crosslinkers. The crosslinker can be any suitablecrosslinker. In some examples, the crosslinker can be incorporated in acrosslinked viscosifier, and in other examples, the crosslinker cancrosslink a crosslinkable material (e.g., downhole). The crosslinker caninclude at least one of chromium, aluminum, antimony, zirconium,titanium, calcium, boron, iron, silicon, copper, zinc, magnesium, and anion thereof. The crosslinker can include at least one of boric acid,borax, a borate, a (C₁-C₃₀)hydrocarbylboronic acid, a(C₁-C₃₀)hydrocarbyl ester of a (C₁-C₃₀)hydrocarbylboronic acid, a(C₁-C₃₀)hydrocarbylboronic acid-modified polyacrylamide, ferricchloride, disodium octaborate tetrahydrate, sodium metaborate, sodiumdiborate, sodium tetraborate, disodium tetraborate, a pentaborate,ulexite, colemanite, magnesium oxide, zirconium lactate, zirconiumtriethanol amine, zirconium lactate triethanolamine, zirconiumcarbonate, zirconium acetylacetonate, zirconium malate, zirconiumcitrate, zirconium diisopropylamine lactate, zirconium glycolate,zirconium triethanol amine glycolate, zirconium lactate glycolate,titanium lactate, titanium malate, titanium citrate, titanium ammoniumlactate, titanium triethanolamine, titanium acetylacetonate, aluminumlactate, and aluminum citrate. In some embodiments, the crosslinker canbe a (C₁-C₂₀)alkylenebiacrylamide (e.g., methylenebisacrylamide), apoly((C₁-C₂₀)alkenyl)-substituted mono- or poly-(C₁-C₂₀)alkyl ether(e.g., pentaerythritol allyl ether), and a poly(C₂-C₂₀)alkenylbenzene(e.g., divinylbenzene). In some embodiments, the crosslinker can be atleast one of alkyl diacrylate, ethylene glycol diacrylate, ethyleneglycol dimethacrylate, polyethylene glycol diacrylate, polyethyleneglycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylatedbisphenol A dimethacrylate, ethoxylated trimethylol propane triacrylate,ethoxylated trimethylol propane trimethacrylate, ethoxylated glyceryltriacrylate, ethoxylated glyceryl trimethacrylate, ethoxylatedpentaerythritol tetraacrylate, ethoxylated pentaerythritoltetramethacrylate, ethoxylated dipentaerythritol hexaacrylate,polyglyceryl monoethylene oxide polyacrylate, polyglyceryl polyethyleneglycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritolhexamethacrylate, neopentyl glycol diacrylate, neopentyl glycoldimethacrylate, pentaerythritol triacrylate, pentaerythritoltrimethacrylate, trimethylol propane triacrylate, trimethylol propanetrimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecanedimethanol dimethacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanedioldimethacrylate. The crosslinker can be about 0.000,01 wt % to about 5 wt% of the composition of a cured product thereof, about 0.001 wt % toabout 0.01 wt %, or about 0.000,01 wt % or less, or about 0.000,05 wt %,0.000,1, 0.000,5, 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, orabout 5 wt % or more.

In some embodiments, the composition or a cured product thereof caninclude one or more breakers. The breaker can be any suitable breaker,such that the surrounding fluid (e.g., a fracturing fluid) can be atleast partially broken for more complete and more efficient recoverythereof, such as at the conclusion of the hydraulic fracturingtreatment. In some embodiments, the breaker can be encapsulated orotherwise formulated to give a delayed-release or a time-release of thebreaker, such that the surrounding liquid can remain viscous for asuitable amount of time prior to breaking. The breaker can be anysuitable breaker; for example, the breaker can be a compound thatincludes a Na⁺, K⁺, Li⁺, Zn⁺, NH₄ ⁺, Fe²⁺, Fe³⁺, Cu¹⁺, Cu²⁺, Ca²⁺, Mg²⁺,Zn²⁺, and an Al³⁺ salt of a chloride, fluoride, bromide, phosphate, orsulfate ion. In some examples, the breaker can be an oxidative breakeror an enzymatic breaker. An oxidative breaker can be at least one of aNa⁺, K⁺, Li⁺, Zn⁺, NH₄ ⁺, Fe²⁺, Fe³⁺, Cu¹⁺, Cu²⁺, Ca²⁺, Mg²⁺, Zn²⁺, andan Al³⁺ salt of a persulfate, percarbonate, perborate, peroxide,perphosphosphate, permanganate, chlorite, or hyperchlorite ion. Anenzymatic breaker can be at least one of an alpha or beta amylase,amyloglucosidase, oligoglucosidase, invertase, maltase, cellulase,hemi-cellulase, and mannanohydrolase. The breaker can be about 0.001 wt% to about 30 wt % of the composition, or about 0.01 wt % to about 5 wt%, or about 0.001 wt % or less, or about 0.005 wt %, 0.01, 0.05, 0.1,0.5, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, orabout 30 wt % or more.

The composition, a cured product thereof, or a mixture including thecomposition or a cured product thereof, can include any suitable fluid.For example, the fluid can be at least one of crude oil, dipropyleneglycol methyl ether, dipropylene glycol dimethyl ether, dipropyleneglycol methyl ether, dipropylene glycol dimethyl ether, dimethylformamide, diethylene glycol methyl ether, ethylene glycol butyl ether,diethylene glycol butyl ether, butylglycidyl ether, propylene carbonate,D-limonene, a C₂-C₄₀ fatty acid C₁-C₁₀ alkyl ester (e.g., a fatty acidmethyl ester), tetrahydrofurfuryl methacrylate, tetrahydrofurfurylacrylate, 2-butoxy ethanol, butyl acetate, butyl lactate, furfurylacetate, dimethyl sulfoxide, dimethyl formamide, a petroleumdistillation product of fraction (e.g., diesel, kerosene, napthas, andthe like) mineral oil, a hydrocarbon oil, a hydrocarbon including anaromatic carbon-carbon bond (e.g., benzene, toluene), a hydrocarbonincluding an alpha olefin, xylenes, an ionic liquid, methyl ethylketone, an ester of oxalic, maleic or succinic acid, methanol, ethanol,propanol (iso- or normal-), butyl alcohol (iso-, tert-, or normal-), analiphatic hydrocarbon (e.g., cyclohexanone, hexane), water, brine,produced water, flowback water, brackish water, and sea water. The fluidcan form about 0.001 wt % to about 99.999 wt % of the composition, acured product thereof, or a mixture including the same, or about 0.001wt % or less, 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30,35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99,99.9, 99.99, or about 99.999 wt % or more.

The composition including the epoxide-containing glycerol ester and thehardening agent, or a cured product thereof, can include any suitabledownhole fluid. The composition including the epoxide-containingglycerol ester and the hardening agent can be combined with any suitabledownhole fluid before, during, or after the placement of the compositionin the subterranean formation or the contacting of the composition andthe subterranean material. In some examples, the composition includingthe epoxide-containing glycerol ester and at least two epoxidesubstituents and the hardening agent is combined with a downhole fluidabove the surface, and then the combined composition is placed in asubterranean formation or contacted with a subterranean material. Inanother example, the composition including the epoxide-containingglycerol ester and the hardening agent is injected into a subterraneanformation to combine with a downhole fluid, and the combined compositionis contacted with a subterranean material or is considered to be placedin the subterranean formation. In various examples, at least one ofprior to, during, and after the placement of the composition in thesubterranean formation or contacting of the subterranean material andthe composition, the composition is used in the subterranean formation(e.g., downhole), at least one of alone and in combination with othermaterials, as a fracturing fluid, spotting fluid, clean-up fluid,completion fluid, remedial treatment fluid, abandonment fluid, pill,cementing fluid, packer fluid, or a combination thereof.

In various embodiments, the composition including the epoxide-containingglycerol ester and the hardening agent, a cured product thereof, or amixture including the same, can include any suitable downhole fluid,such as an aqueous or oil-based fluid including a fracturing fluid,spotting fluid, clean-up fluid, completion fluid, remedial treatmentfluid, abandonment fluid, pill, cementing fluid, packer fluid, or acombination thereof. The placement of the composition in thesubterranean formation can include contacting the subterranean materialand the mixture. Any suitable weight percent of the composition, curedproduct thereof, or a mixture including the same that is placed in thesubterranean formation or contacted with the subterranean material canbe the downhole fluid, such as about 0.001 wt % to about 99.999 wt %,about 0.01 wt % to about 99.99 wt %, about 0.1 wt % to about 99.9 wt %,about 20 wt % to about 90 wt %, or about 0.001 wt % or less, or about0.01 wt %, 0.1, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 85,90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99 wt %, or about99.999 wt %.

In some embodiments, the composition, a cured product thereof, or amixture including the same can include any suitable amount of anysuitable material used in a downhole fluid. For example, the compositionor a cured product thereof can include water, saline, aqueous base,acid, oil, organic solvent, synthetic fluid oil phase, aqueous solution,alcohol or polyol, cellulose, starch, alkalinity control agents, aciditycontrol agents, density control agents, density modifiers, emulsifiers,dispersants, polymeric stabilizers, crosslinking agents, polyacrylamide,a polymer or combination of polymers, antioxidants, heat stabilizers,foam control agents, solvents, diluents, plasticizer, filler orinorganic particle, pigment, dye, precipitating agent, rheologymodifier, oil-wetting agents, set retarding additives, surfactants,gases, weight reducing additives, heavy-weight additives, lostcirculation materials, filtration control additives, salts, fibers,thixotropic additives, breakers, crosslinkers, rheology modifiers,curing accelerators, curing retarders, pH modifiers, chelating agents,scale inhibitors, enzymes, resins, water control materials, oxidizers,markers, Portland cement, pozzolana cement, gypsum cement, high aluminacontent cement, slag cement, silica cement, fly ash, metakaolin, shale,zeolite, a crystalline silica compound, amorphous silica, hydratableclays, microspheres, pozzolan lime, or a combination thereof. In variousembodiments, the composition or a cured product thereof can include oneor more additive components such as: thinner additives such asCOLDTROL®, ATC®, OMC 2™, and OMC 42™; RHEMOD™, a viscosifier andsuspension agent including a modified fatty acid; additives forproviding temporary increased viscosity, such as for shipping (e.g.,transport to the well site) and for use in sweeps (for example,additives having the trade name TEMPERUS™ (a modified fatty acid) andVIS-PLUS®, a thixotropic viscosifying polymer blend); TAU-MOD™, aviscosifying/suspension agent including an amorphous/fibrous material;additives for filtration control, for example, ADAPTA®, a hightemperature high pressure (HTHP) filtration control agent including acrosslinked copolymer; DURATONE® HT, a filtration control agent thatincludes an organophilic lignite, more particularly organophilicleonardite; THERMO TONE™, a HTHP filtration control agent including asynthetic polymer; BDF™-366, a HTHP filtration control agent; BDF™-454,a HTHP filtration control agent; LIQUITONE™, a polymeric filtrationagent and viscosifier; additives for HTHP emulsion stability, forexample, FACTANT™, which includes highly concentrated tall oilderivative; emulsifiers such as LE SUPERMUL™ and EZ MUL® NT,polyaminated fatty acid emulsifiers, and FORTI-MUL®; DRIL TREAT®, an oilwetting agent for heavy fluids; BARACARB®, a sized ground marblebridging agent; BAROID®, a ground barium sulfate weighting agent;BAROLIFT®, a hole sweeping agent; SWEEP-WATE®, a sweep weighting agent;BDF-508, a diamine dimer rheology modifier; GELTONE® II organophilicclay; BAROFIBRE™ O for lost circulation management and seepage lossprevention, including a natural cellulose fiber; STEELSEAL®, a resilientgraphitic carbon lost circulation material; HYDRO-PLUG®, a hydratableswelling lost circulation material; lime, which can provide alkalinityand can activate certain emulsifiers; and calcium chloride, which canprovide salinity. Any suitable proportion of the composition, curedproduct thereof, or mixture including the composition or cured productthereof can include any optional component listed in this paragraph,such as about 0.001 wt % to about 99.999 wt %, about 0.01 wt % to about99.99 wt %, about 0.1 wt % to about 99.9 wt %, about 20 to about 90 wt%, or about 0.001 wt % or less, or about 0.01 wt %, 0.1, 1, 2, 3, 4, 5,10, 15, 20, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97,98, 99, 99.9, 99.99 wt %, or about 99.999 wt % or more.

A pill is a relatively small quantity (e.g., less than about 500 bbl, orless than about 200 bbl) of drilling fluid used to accomplish a specifictask that the regular drilling fluid cannot perform. For example, a pillcan be a high-viscosity pill to, for example, help lift cuttings out ofa vertical wellbore. In another example, a pill can be a freshwater pillto, for example, dissolve a salt formation. Another example is apipe-freeing pill to, for example, destroy filter cake and relievedifferential sticking forces. In another example, a pill is a lostcirculation material pill to, for example, plug a thief zone. A pill caninclude any component described herein as a component of a downholefluid.

A cement fluid can include an aqueous mixture of at least one of cementand cement kiln dust. The composition including the epoxide-containingglycerol ester and the hardening agent, or a cured product thereof, canform a useful combination with cement or cement kiln dust. The cementkiln dust can be any suitable cement kiln dust. Cement kiln dust can beformed during the manufacture of cement and can be partially calcinedkiln feed that is removed from the gas stream and collected in a dustcollector during a manufacturing process. Cement kiln dust can beadvantageously utilized in a cost-effective manner since kiln dust isoften regarded as a low value waste product of the cement industry. Someembodiments of the cement fluid can include cement kiln dust but nocement, cement kiln dust and cement, or cement but no cement kiln dust.The cement can be any suitable cement. The cement can be a hydrauliccement. A variety of cements can be utilized in accordance withembodiments of the present invention; for example, those includingcalcium, aluminum, silicon, oxygen, iron, or sulfur, which can set andharden by reaction with water. Suitable cements can include Portlandcements, pozzolana cements, gypsum cements, high alumina contentcements, slag cements, silica cements, and combinations thereof In someembodiments, the Portland cements that are suitable for use inembodiments of the present invention are classified as Classes A, C, H,and G cements according to the American Petroleum Institute. A cementcan be generally included in the cementing fluid in an amount sufficientto provide the desired compressive strength, density, or cost. In someembodiments, the hydraulic cement can be present in the cementing fluidin an amount in the range of from 0 wt % to about 100 wt %, about 0 wt %to about 95 wt %, about 20 wt % to about 95 wt %, or about 50 wt % toabout 90 wt %. A cement kiln dust can be present in an amount of atleast about 0.01 wt %, or about 5 wt % to about 80 wt %, or about 10 wt% to about 50 wt %.

Optionally, other additives can be added to a cement or kilndust-containing composition of embodiments of the present invention asdeemed appropriate by one skilled in the art, with the benefit of thisdisclosure. Any optional ingredient listed in this paragraph can beeither present or not present in the composition or a cured productthereof For example, the composition can include fly ash, metakaolin,shale, zeolite, set retarding additive, surfactant, a gas, accelerators,weight reducing additives, heavy-weight additives, lost circulationmaterials, filtration control additives, dispersants, and combinationsthereof In some examples, additives can include crystalline silicacompounds, amorphous silica, salts, fibers, hydratable clays,microspheres, pozzolan lime, thixotropic additives, combinationsthereof, and the like.

System or Apparatus.

In various embodiments, the present invention provides a system. Thesystem can be any suitable system that can use or that can be generatedby use of an embodiment of the composition described herein in asubterranean formation, or that can perform or be generated byperformance of a method for using the composition described herein. Thesystem can include a composition including the epoxide-containingglycerol ester and the hardening agent. The system can also include asubterranean formation including the composition therein. In someembodiments, the system includes a cured product of a compositionincluding the epoxide-containing glycerol ester and the hardening agent,and a subterranean formation including the composition therein, such asa consolidated proppant, gravel, or sand pack in the subterraneanformation that is consolidated with a cured product of the composition.In some embodiments, the composition in the system can also include adownhole fluid, or the system can include a mixture of the compositionand downhole fluid. In some embodiments, the system can include atubular, and a pump configured to pump the composition into thesubterranean formation through the tubular.

Various embodiments provide systems and apparatus configured fordelivering the composition described herein to a subterranean locationand for using the composition therein, such as for a fracturingoperation (e.g., pre-pad, pad, slurry, or finishing stages). In variousembodiments, the system or apparatus can include a pump fluidly coupledto a tubular (e.g., any suitable type of oilfield pipe, such aspipeline, drill pipe, production tubing, and the like), the tubularcontaining a composition including the epoxide-containing glycerol esterand the hardening agent.

In some embodiments, the system can include a drillstring disposed in awellbore, the drillstring including a drill bit at a downhole end of thedrillstring. The system can also include an annulus between thedrillstring and the wellbore. The system can also include a pumpconfigured to circulate the composition through the drill string,through the drill bit, and back above-surface through the annulus. Insome embodiments, the system can include a fluid processing unitconfigured to process the composition exiting the annulus to generate acleaned drilling fluid for recirculation through the wellbore.

In various embodiments, the present invention provides an apparatus. Theapparatus can be any suitable apparatus that can use or that can begenerated by use of the composition or cured product thereof describedherein in a subterranean formation, or that can perform or be generatedby performance of a method for using the composition or cured productthereof described herein.

The pump can be a high pressure pump in some embodiments. As usedherein, the term “high pressure pump” will refer to a pump that iscapable of delivering a fluid to a subterranean formation (e.g.,downhole) at a pressure of about 1000 psi or greater. A high pressurepump can be used when it is desired to introduce the composition to asubterranean formation at or above a fracture gradient of thesubterranean formation, but it can also be used in cases wherefracturing is not desired. In some embodiments, the high pressure pumpcan be capable of fluidly conveying particulate matter, such as proppantparticulates, into the subterranean formation. Suitable high pressurepumps will be known to one having ordinary skill in the art and caninclude floating piston pumps and positive displacement pumps.

In other embodiments, the pump can be a low pressure pump. As usedherein, the term “low pressure pump” will refer to a pump that operatesat a pressure of about 1000 psi or less. In some embodiments, a lowpressure pump can be fluidly coupled to a high pressure pump that isfluidly coupled to the tubular. That is, in such embodiments, the lowpressure pump can be configured to convey the composition to the highpressure pump. In such embodiments, the low pressure pump can “step up”the pressure of the composition before it reaches the high pressurepump.

In some embodiments, the systems or apparatuses described herein canfurther include a mixing tank that is upstream of the pump and in whichthe composition is formulated. In various embodiments, the pump (e.g., alow pressure pump, a high pressure pump, or a combination thereof) canconvey the composition from the mixing tank or other source of thecomposition to the tubular. In other embodiments, however, thecomposition can be formulated offsite and transported to a worksite, inwhich case the composition can be introduced to the tubular via the pumpdirectly from its shipping container (e.g., a truck, a railcar, a barge,or the like) or from a transport pipeline. In either case, thecomposition can be drawn into the pump, elevated to an appropriatepressure, and then introduced into the tubular for delivery to thesubterranean formation.

FIG. 1 shows an illustrative schematic of systems and apparatuses thatcan deliver embodiments of the compositions of the present invention toa subterranean location, according to one or more embodiments. It shouldbe noted that while FIG. 1 generally depicts a land-based system orapparatus, it is to be recognized that like systems and apparatuses canbe operated in subsea locations as well. Embodiments of the presentinvention can have a different scale than that depicted in FIG. 1. Asdepicted in FIG. 1, system or apparatus 1 can include mixing tank 10, inwhich an embodiment of the composition can be formulated. Thecomposition can be conveyed via line 12 to wellhead 14, where thecomposition enters tubular 16, with tubular 16 extending from wellhead14 into subterranean formation 18. Upon being ejected from tubular 16,the composition can subsequently penetrate into subterranean formation18. Pump 20 can be configured to raise the pressure of the compositionto a desired degree before its introduction into tubular 16. It is to berecognized that system or apparatus 1 is merely exemplary in nature andvarious additional components can be present that have not necessarilybeen depicted in FIG. 1 in the interest of clarity. In some examples,additional components that can be present include supply hoppers,valves, condensers, adapters, joints, gauges, sensors, compressors,pressure controllers, pressure sensors, flow rate controllers, flow ratesensors, temperature sensors, and the like.

Although not depicted in FIG. 1, at least part of the composition can,in some embodiments, flow back to wellhead 14 and exit subterraneanformation 18. The composition that flows back can be substantiallydiminished in the concentration of various components therein. In someembodiments, the composition that has flowed back to wellhead 14 cansubsequently be recovered, and in some examples reformulated, andrecirculated to subterranean formation 18.

It is also to be recognized that the disclosed composition can alsodirectly or indirectly affect the various downhole or subterraneanequipment and tools that can come into contact with the compositionduring operation. Such equipment and tools can include wellbore casing,wellbore liner, completion string, insert strings, drill string, coiledtubing, slickline, wireline, drill pipe, drill collars, mud motors,downhole motors and/or pumps, surface-mounted motors and/or pumps,centralizers, turbolizers, scratchers, floats (e.g., shoes, collars,valves, and the like), logging tools and related telemetry equipment,actuators (e.g., electromechanical devices, hydromechanical devices, andthe like), sliding sleeves, production sleeves, plugs, screens, filters,flow control devices (e.g., inflow control devices, autonomous inflowcontrol devices, outflow control devices, and the like), couplings(e.g., electro-hydraulic wet connect, dry connect, inductive coupler,and the like), control lines (e.g., electrical, fiber optic, hydraulic,and the like), surveillance lines, drill bits and reamers, sensors ordistributed sensors, downhole heat exchangers, valves and correspondingactuation devices, tool seals, packers, cement plugs, bridge plugs, andother wellbore isolation devices or components, and the like. Any ofthese components can be included in the systems and apparatusesgenerally described above and depicted in FIG. 1.

Composition for Treatment of a Subterranean Formation.

Various embodiments provide a composition for treatment of asubterranean formation. The composition can be any suitable compositionthat can be used to perform an embodiment of the method for treatment ofa subterranean formation described herein. For example, the compositioncan include the epoxide-containing glycerol ester and the hardeningagent. Various embodiments of the present invention provide a curedproduct of the composition that includes the epoxide-containing glycerolester and the hardening agent.

In some embodiments, the composition or cured product thereof furtherincludes a downhole fluid. The downhole fluid can be any suitabledownhole fluid. In some embodiments, the downhole fluid is a compositionfor fracturing of a subterranean formation or subterranean material, ora fracturing fluid. The composition can include a proppant or gravel,such as proppant or gravel having a mixture of components including theepoxide-containing glycerol ester and the hardening agent.

Method for Preparing a Composition for Treatment of a SubterraneanFormation.

In various embodiments, the present invention provides a method forpreparing a composition for treatment of a subterranean formation. Themethod can be any suitable method that produces an embodiment of thecomposition described herein. For example, the method can includeforming a composition including the epoxide-containing glycerol esterand the hardening agent.

The terms and expressions that have been employed are used as terms ofdescription and not of limitation, and there is no intention in the useof such terms and expressions of excluding any equivalents of thefeatures shown and described or portions thereof, but it is recognizedthat various modifications are possible within the scope of theembodiments of the present invention. Thus, it should be understood thatalthough the present invention has been specifically disclosed byspecific embodiments and optional features, modification and variationof the concepts herein disclosed may be resorted to by those of ordinaryskill in the art, and that such modifications and variations areconsidered to be within the scope of embodiments of the presentinvention.

Additional Embodiments

The following exemplary embodiments are provided, the numbering of whichis not to be construed as designating levels of importance:

Embodiment 1 provides a method of treating a subterranean formation, themethod comprising:

placing in a subterranean formation a composition comprising

-   -   a glycerol ester comprising at least two epoxides; and    -   a hardening agent.

Embodiment 2 provides the method of Embodiment 1, wherein the methodfurther comprises obtaining or providing the composition, wherein theobtaining or providing of the composition occurs above-surface.

Embodiment 3 provides the method of any one of Embodiments 1-2, whereinthe method further comprises obtaining or providing the composition,wherein the obtaining or providing of the composition occurs in thesubterranean formation.

Embodiment 4 provides the method of any one of Embodiments 1-3, furthercomprising consolidating particulates in the subterranean formation witha cured product of the composition.

Embodiment 5 provides the method of Embodiment 1-4, further comprisingat least partially curing the composition, to form a cured product ofthe composition.

Embodiment 6 provides the method of Embodiment 5, wherein the curingoccurs in the subterranean formation.

Embodiment 7 provides the method of any one of Embodiments 1-6, whereinthe composition further comprises at least one of proppant and gravel.

Embodiment 8 provides the method of Embodiment 7, wherein the proppantor gravel is about 1 wt % to about 90 wt % of the composition.

Embodiment 9 provides the method of any one of Embodiments 7-8, whereinthe proppant or gravel is about 5 wt % to about 70 wt % of thecomposition.

Embodiment 10 provides the method of any one of Embodiments 7-9, whereinthe composition is at least partially coated on the proppant or gravel.

Embodiment 11 provides the method of any one of Embodiments 1-10,comprising placing the composition in at least one of a fracture andflowpath in the subterranean formation.

Embodiment 12 provides the method of Embodiment 11, wherein the fractureis present in the subterranean formation when the composition is placedin the subterranean formation.

Embodiment 13 provides the method of any one of Embodiments 11-12,wherein the method comprises forming the fracture or flowpath.

Embodiment 14 provides the method of any one of Embodiments 1-13,further comprising fracturing the subterranean formation to form atleast one fracture in the subterranean formation.

Embodiment 15 provides the method of any one of Embodiments 1-14,wherein the glycerol ester comprising at least two epoxides is about0.001 wt % to about 50 wt % of the composition.

Embodiment 16 provides the method of any one of Embodiments 1-15,wherein the glycerol ester comprising at least two epoxides is about0.01 wt % to about 30 wt % of the composition.

Embodiment 17 provides the method of any one of Embodiments 1-16,wherein the hardening agent is about 0.001 wt % to about 50 wt % of thecomposition.

Embodiment 18 provides the method of any one of Embodiments 1-17,wherein the hardening agent is about 0.01 wt % to about 30 wt % of thecomposition.

Embodiment 19 provides the method of any one of Embodiments 1-18,wherein the composition further comprises a carrier liquid.

Embodiment 20 provides the method of any one of Embodiments 1-19,wherein the glycerol ester is at least one of a mono-, di-, ortri-glyceride.

Embodiment 21 provides the method of any one of Embodiments 1-20,wherein the glycerol ester is a fatty acid glycerol ester.

Embodiment 22 provides the method of any one of Embodiments 1-21,wherein the glycerol ester comprising at least two epoxides has thefollowing structure:

wherein

-   -   R¹, R², and R³ are independently chosen from —H, substituted or        unsubstituted (C₁-C₆₀)hydrocarbyl, and R⁴,    -   wherein        -   R⁴ at each occurrence is independently            —C(O)—(C₂-C₆₀)hydrocarbyl comprising at least two oxygen            atoms each independently directly attached to two different            adjacent carbon atoms of the (C₂-C₆₀)hydrocarbyl,        -   the (C₁-C₆₀)hydrocarbyl and the (C₂-C₆₀)hydrocarbyl are            independently interrupted by 0, 1, 2, or 3 groups            independently chosen from —O—, —S—, and substituted or            unsubstituted —NH—, and        -   at least one of R¹, R², and R³ is R⁴.

Embodiment 23 provides the method of Embodiment 22, wherein each of R¹,R², and R³ are independently selected from R⁴ and —H.

Embodiment 24 provides the method of any one of Embodiments 22-23,wherein at least two of R¹, R², and R³ are R⁴.

Embodiment 25 provides the method of any one of Embodiments 22-24,wherein each of R¹, R², and R³ is R⁴.

Embodiment 26 provides the method of any one of Embodiments 22-25,wherein

R¹, R², and R³ are independently chosen from —H, substituted orunsubstituted (C₅-C₆₀)alkyl, substituted or unsubstituted—C(O)—(C₄-C₅₉)alkyl substituted or unsubstituted (C₅-C₆₀)alkenyl,substituted or unsubstituted —C(O)—(C₄-C₅₉)alkenyl, and R⁴,

the (C₅-C₆₀)alkenyl and the —C(O)—(C₄-C₅₉)alkenyl each independentlycomprise about 1 to about 29 carbon-carbon double bonds, and

the (C₅-C₆₀)alkyl, the —C(O)—(C₄-C₅₉)alkyl, the (C₅-C₆₀)alkenyl, and the—C(O)—(C₄-C₅₉)alkenyl each independently comprise about 2 to about 30oxygen atoms each independently directly bound to two different adjacentcarbon atoms of the (C₅-C₆₀)alkyl, the —C(O)—(C₄-C₅₉)alkyl, and the(C₅-C₆₀)alkenyl.

Embodiment 27 provides the method of any one of Embodiments 22-26,wherein

R⁴ at each occurrence is independently chosen from —C(O)—(C₂-C₆₀)alkyland —C(O)—(C₂-C₆₀)alkenyl, and

the (C₂-C₆₀)alkyl and the (C₂-C₆₀)alkenyl each independently compriseabout 2 to about 30 oxygen atoms each independently directly bound totwo different adjacent carbon atoms of the (C₂-C₆₀)alkyl and the(C₂-C₆₀)alkenyl.

Embodiment 28 provides the method of any one of Embodiments 1-27,wherein the glycerol ester comprising at least two epoxides is an oilcomprising at least one epoxidized aliphatic carbon-carbon double bond.

Embodiment 29 provides the method of any one of Embodiments 1-28,wherein the glycerol ester comprising at least two epoxides is an oilthat has been epoxided, wherein the oil is chosen from ester chosen fromaçai oil, almond oil, amaranth oil, apple seed oil, apricot oil, arganoil, avocado oil, babassu oil, beech nut oil, ben oil, bitter gourd oil,black seed oil, blackcurrant seed oil, borage seed oil, borneo tallownut oil, bottle gourd oil, buffalo gourd oil, butternut squash seed oil,camelina sativa oil, cape chestnut oil, carob pod oil, cashew oil,cocklebur oil, cocoa butter, coconut oil, cohune oil, coriander seedoil, corn oil, cottonseed oil, date seed oil, dika oil, egusi seed oil,evening primrose oil, flaxseed oil, grape seed oil, grapefruit seed oil,hazelnut oil, hemp oil, kapok seed oil, kenaf seed oil, lallemantia oil,linseed oil, macadamia oil, mafura oil, manila oil, meadowfoam seed oil,mongongo nut oil, mustard oil, niger seed oil, okra seed oil, olive oil,orange oil, palm oil, papaya seed oil, peanut oil, pecan oil, pequi oil,perilla seed oil, persimmon seed oil, pili nut oil, pistachio oil,pomegranate seed oil, poppyseed oil, prune kernel oil, pumpkin seed oil,quinoa oil, ramtil oil, rapeseed oil, rice bran oil, royle oil,safflower oil, sapote oil, seje oil, sesame oil, shea butter, soybeanoil, sunflower oil, taramira oil, tea seed oil, thistle oil, tigernutoil, tobacco seed oil, tomato seed oil, walnut oil, watermelon seed oil,wheat germ oil, one or more fractions thereof, or a combination thereof.

Embodiment 30 provides the method of any one of Embodiments 1-29,wherein the glycerol ester comprising at least two epoxides is an oilthat has been epoxided, wherein the oil is chosen from agarwood oil,allspice oil, almond oil, anise oil, basil oil, bay leaf oil, benzoinoil, bergamot oil, buchu oil, camphor oil, cannabis oil, cassia oil,cedar oil, celery oil, chamomile oil, cinnamon oil, clary sage oil,clove oil, copaiba oil, cumin oil, eucalyptus oil, frankincense oil,galangal oil, geranium oil, ginger oil, grapefruit oil, guava oil, hopsoil, hyssop oil, jasmine oil, juniper oil, lavender oil, lemon grassoil, lemon oil, lemongrass oil, lime oil, manuka oil, mandarin orange,marjoram oil, melaleuca oil, myrrh oil, nutmeg oil, orange oil, oreganooil, patchouli oil, peppermint oil, pine oil, rose oil, rosehip oil,rosemary oil, rosewood oil, sage oil, sandalwood oil, sassafras oil,spearmint oil, tangerine oil, tea tree oil, thyme oil, tsuga oil,valerian oil, vanilla oil, wintergreen oil, ylang-ylang oil, one or morefractions thereof, or a combination thereof.

Embodiment 31 provides the method of any one of Embodiments 1-30,wherein the glycerol ester comprising at least two epoxides is an atleast partially epoxidized oil chosen from soybean oil and linseed oil.

Embodiment 32 provides the method of any one of Embodiments 1-31,wherein the glycerol ester comprising at least two epoxides is

Embodiment 33 provides the method of any one of Embodiments 1-32,wherein the glycerol ester comprising at least two epoxides is

Embodiment 34 provides the method of any one of Embodiments 1-33,wherein the glycerol ester comprising at least two epoxides has anepoxide equivalent weight of about 50 g/mol to about 1000 g/mol.

Embodiment 35 provides the method of any one of Embodiments 1-34,wherein the glycerol ester comprising at least two epoxides has anepoxide equivalent weight of about 100 g/mol to about 500 g/mol.

Embodiment 36 provides the method of any one of Embodiments 1-35,wherein the hardening agent comprises at least one primary or secondaryamine.

Embodiment 37 provides the method of any one of Embodiments 1-36,wherein the hardening agent comprises at least one of an amine, anaromatic amine, an aliphatic amine, a cyclo-aliphatic amine, apolyamine, an amide, and a polyamide.

Embodiment 38 provides the method of any one of Embodiments 1-37,wherein the hardening agent is selected from the group consisting ofdiethylene tetramine, ethylene diamine, polyethyleneimine, piperidine,triethylamine, benzyldimethylamine, N,N-dimethylaminopyridine,2-(N,N-dimethylaminomethyl)phenol, tris(dimethylaminomethyl)phenol,N-2-(aminoethyl)-3-aminopropyltrimethoxysilane,3-glycidoxypropyltrimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane, piperazine, aminoethylpiperazine, pyrrole, imidazole,pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine,isoindole, indole, indazole, purine, quinolizine, quinoline,isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline,carbazole, carbazole, phenanthridine, acridine, phenathroline,phenazine, imidazolidine, phenoxazine, cinnoline, pyrrolidine,pyrroline, imidazoline, piperidine, indoline, isoindoline,quinuclindine, morpholine, azocine, azepine, azepine, 1,3,5-triazine,thiazole, pteridine, dihydroquinoline, hexamethyleneimine, indazole,polyethyleneimine, 2-ethyl-4-methyl imidazole,1,1,3-trichlorotrifluoroacetone, a substituted or unsubstitutedderivative of any one thereof, and combinations thereof.

Embodiment 39 provides the method of any one of Embodiments 1-38,wherein the composition further comprises a silane coupling agent.

Embodiment 40 provides the method of any one of Embodiments 1-39,wherein the composition further comprises a surfactant.

Embodiment 41 provides the method of any one of Embodiments 1-40,wherein the composition further comprises a hydrolyzable ester.

Embodiment 42 provides the method of any one of Embodiments 1-41,wherein the composition further comprises at least one tackifier.

Embodiment 43 provides the method of any one of Embodiments 1-42,wherein the composition further comprises a curing agent.

Embodiment 44 provides the method of any one of Embodiments 1-43,further comprising combining the composition with an aqueous oroil-based fluid comprising a fracturing fluid, spotting fluid, clean-upfluid, completion fluid, remedial treatment fluid, abandonment fluid,pill, cementing fluid, packer fluid, or a combination thereof, to form amixture, wherein the placing the composition in the subterraneanformation comprises placing the mixture in the subterranean formation.

Embodiment 45 provides the method of any one of Embodiments 1-44,wherein at least one of prior to, during, and after the placing of thecomposition in the subterranean formation, the composition is used inthe subterranean formation, at least one of alone and in combinationwith other materials, as a fracturing fluid, spotting fluid, clean-upfluid, completion fluid, remedial treatment fluid, abandonment fluid,pill, cementing fluid, packer fluid, or a combination thereof.

Embodiment 46 provides the method of any one of Embodiments 1-45,wherein the composition further comprises water, saline, aqueous base,oil, organic solvent, synthetic fluid oil phase, aqueous solution,alcohol or polyol, cellulose, starch, alkalinity control agent, aciditycontrol agent, density control agent, density modifier, emulsifier,dispersant, polymeric stabilizer, crosslinking agent, polyacrylamide,polymer or combination of polymers, antioxidant, heat stabilizer, foamcontrol agent, solvent, diluent, plasticizer, filler or inorganicparticle, pigment, dye, precipitating agent, rheology modifier,oil-wetting agent, set retarding additive, surfactant, corrosioninhibitor, gas, weight reducing additive, heavy-weight additive, lostcirculation material, filtration control additive, salt, fiber,thixotropic additive, breaker, crosslinker, gas, rheology modifier,curing accelerator, curing retarder, pH modifier, chelating agent, scaleinhibitor, enzyme, resin, water control material, polymer, oxidizer, amarker, Portland cement, pozzolana cement, gypsum cement, high aluminacontent cement, slag cement, silica cement, fly ash, metakaolin, shale,zeolite, a crystalline silica compound, amorphous silica, fibers, ahydratable clay, microspheres, pozzolan lime, or a combination thereof.

Embodiment 47 provides a system for performing the method of any one ofEmbodiments 1-46, the system comprising:

a tubular disposed in the subterranean formation; and

a pump configured to pump the composition in the subterranean formationthrough the tubular.

Embodiment 48 provides a method of treating a subterranean formation,the method comprising:

placing in a subterranean formation a composition comprising

-   -   a glycerol ester comprising at least two epoxides having the        structure:

-   -   wherein        -   R¹, R², and R³ are independently chosen from            —C(O)—(C₂-C₆₀)alkyl and —C(O)—(C₂-C₆₀)alkenyl, and        -   in at least one of R¹, R², and R³, the (C₂-C₆₀)alkyl and the            (C₂-C₆₀)alkenyl each independently comprise about 2 to about            30 oxygen atoms each independently directly bound to two            different adjacent carbon atoms of R¹, R², and R³, the            (C₂-C₆₀)alkyl and the (C₂-C₆₀)alkenyl; and    -   an amine-functional hardening agent.

Embodiment 49 provides a system comprising:

a composition comprising

-   -   a glycerol ester comprising at least two epoxides; and    -   a hardening agent; and

a subterranean formation comprising the composition therein.

Embodiment 50 provides the system of Embodiment 49, further comprising

a tubular disposed in the subterranean formation; and

a pump configured to pump the composition in the subterranean formationthrough the tubular.

Embodiment 51 provides a composition for treatment of a subterraneanformation, the composition comprising:

a glycerol ester comprising at least two epoxides; and

a hardening agent.

Embodiment 52 provides the composition of Embodiment 51, wherein thecomposition further comprises a downhole fluid.

Embodiment 53 provides a cured product of the composition of any one ofEmbodiments 51-52.

Embodiment 54 provides a method of preparing a composition for treatmentof a subterranean formation, the method comprising:

forming a composition comprising

-   -   a glycerol ester comprising at least two epoxides; and    -   a hardening agent.

Embodiment 55 provides the composition, method, or system of any one orany combination of Embodiments 1-54 optionally configured such that allelements or options recited are available to use or select from.

1.-54. (canceled)
 55. A method for treating a subterranean formation,comprising: placing a composition into the subterranean formation, thecomposition comprises: a glycerol ester comprising at least twoepoxides; and a hardening agent.
 56. The method of claim 55, furthercomprising consolidating particulates in the subterranean formation witha cured product of the composition.
 57. The method of claim 55, whereinthe composition is at least partially coated on at least one ofproppant, gravel, or a combination thereof, and wherein the proppant orgravel is about 5 wt % to about 70 wt % of the composition.
 58. Themethod of claim 57, further comprising: forming a fracture in thesubterranean formation; and placing the composition and the proppant orgravel in the fracture.
 59. The method of claim 55, wherein thehardening agent is about 0.01 wt % to about 30 wt % of the composition.60. The method of claim 55, wherein the glycerol ester comprising atleast two epoxides has an epoxide equivalent weight of about 100 g/molto about 500 g/mol.
 61. The method of claim 55, wherein the glycerolester comprises a fatty acid glycerol ester.
 62. The method of claim 55,wherein the glycerol ester comprising at least two epoxides has thefollowing structure:

wherein: each R¹, R², and R³ is independently selected from the groupconsisting of —H, substituted or unsubstituted (C₁-C₆₀)hydrocarbyl, andR⁴, wherein: R⁴ at each occurrence is independently—C(O)—(C₂-C₆₀)hydrocarbyl comprising at least two oxygen atoms eachindependently directly attached to two different adjacent carbon atomsof the (C₂-C₆₀)hydrocarbyl, the (C₁-C₆₀)hydrocarbyl and the(C₂-C₆₀)hydrocarbyl are independently interrupted by 0, 1, 2, or 3groups independently chosen from —O—, —S—, and substituted orunsubstituted —NH—, and at least one of R¹, R², and R³ is R⁴.
 63. Themethod of claim 62, wherein each of R¹, R², and R³ are independentlyselected from R⁴ and —H.
 64. The method of claim 62, wherein at leasttwo of R¹, R², and R³ are R⁴.
 65. The method of claim 62, wherein eachof R¹, R², and R³ is R⁴.
 66. The method of claim 62, wherein: R¹, R²,and R³ are independently chosen from —H, substituted or unsubstituted(C₅-C₆₀)alkyl, substituted or unsubstituted —C(O)—(C₄-C₅₉)alkylsubstituted or unsubstituted (C₅-C₆₀)alkenyl, substituted orunsubstituted —C(O)—(C₄-C₅₉)alkenyl, and R⁴, the (C₅-C₆₀)alkenyl and the—C(O)—(C₄-C₅₉)alkenyl each independently comprise about 1 to about 29carbon-carbon double bonds, and the (C₅-C₆₀)alkyl, the—C(O)—(C₄-C₅₉)alkyl, the (C₅-C₆₀)alkenyl, and the —C(O)—(C₄-C₅₉)alkenyleach independently comprise about 2 to about 30 oxygen atoms eachindependently directly bound to two different adjacent carbon atoms ofthe (C₅-C₆₀)alkyl, the —C(O)—(C₄-C₅₉)alkyl, the (C₅-C₆₀)alkenyl, and the—C(O)—(C₄-C₅₉)alkenyl.
 67. The method of claim 62, wherein: R⁴ at eachoccurrence is independently chosen from —C(O)—(C₂-C₆₀)alkyl and—C(O)—(C₂-C₆₀)alkenyl, and the (C₂-C₆₀)alkyl and the (C₂-C₆₀)alkenyleach independently comprise about 2 to about 30 oxygen atoms eachindependently directly bound to two different adjacent carbon atoms ofthe —C(O)—(C₂-C₆₀)alkyl and —C(O)—(C₂-C₆₀)alkenyl.
 68. The method ofclaim 55, wherein the glycerol ester comprising at least two epoxides isan at least partially epoxidized oil chosen from soybean oil and linseedoil.
 69. The method of claim 55, wherein the glycerol ester comprisingat least two epoxides comprises:


70. The method of claim 55, wherein the glycerol ester comprising atleast two epoxides comprises:


71. The method of claim 55, wherein the hardening agent is selected fromthe group consisting of diethylene tetramine, ethylene diamine,polyethyleneimine, piperidine, triethylamine, benzyldimethylamine,N,N-dimethylaminopyridine, 2-(N,N-dimethylaminomethyl)phenol,tris(dimethylaminomethyl)phenol,N-2-(aminoethyl)-3-aminopropyltrimethoxysilane,3-glycidoxypropyltrimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane, piperazine, aminoethylpiperazine, pyrrole, imidazole,pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine,isoindole, indole, indazole, purine, quinolizine, quinoline,isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline,carbazole, carbazole, phenanthridine, acridine, phenathroline,phenazine, imidazolidine, phenoxazine, cinnoline, pyrrolidine,pyrroline, imidazoline, piperidine, indoline, isoindoline,quinuclindine, morpholine, azocine, azepine, azepine, 1,3,5-triazine,thiazole, pteridine, dihydroquinoline, hexamethyleneimine, indazole,polyethyleneimine, 2-ethyl-4-methyl imidazole,1,1,3-trichlorotrifluoroacetone, and any combination thereof.
 72. Asystem for performing the method of claim 55, the system comprising: atubular disposed in the subterranean formation; and a pump configured topump the composition in the subterranean formation through the tubular.73. A method for treating a subterranean formation, comprising: placingproppant or gravel coated with a composition into the subterraneanformation, the composition comprises: a glycerol ester; and a hardeningagent, wherein the glycerol ester comprises:

or a combination thereof; and forming a fracture in the subterraneanformation.
 74. A composition for treatment of a subterranean formation,comprising: a glycerol ester; and a hardening agent, wherein theglycerol ester comprises:

or a combination thereof.